Organic polymers and novel polymerizable compounds

ABSTRACT

Organic polymers having water contact angles of 20° or smaller, preferably 7° or smaller and equipped with both high wettability and high transparency. The organic polymers may contain as partial structures polar structures of about 3 debyes or higher in dipole moment and are available especially from polymerization of polymerizable compounds having alkylene(thio)urea structures.

TECHNICAL FIELD

This invention relates to organic polymers having high waterwettability, molded or otherwise formed products comprising the organicpolymers, novel polymerizable compounds and compositions capable ofaffording organic polymers having high water wettability, andantifouling materials, anti-mist materials, dew preventing materials,water (liquid) absorbent materials and optical materials, all of whichmake use of organic polymers and molded or otherwise formed productshaving high water wettability.

BACKGROUND ART

As a representative physical value expressing water wettability, watercontact angle is known. In general, those having water contact angles ofless than 90° are classified as hydrophilic materials, and those havingwater contact angles of greater than 90° are classified as waterrepellant materials. As the water contact angle approaches from 90°toward 0°, the material can be considered to be higher in waterwettability.

High water wettability is extremely effective for water retainingmaterials or the like, which are useful, for example, for the inhibitionof dew-induced misting of windowpanes, mirrors, agricultural vinylsheets, eyeglass lenses, camera lenses and the like, for the suppressionof a reduction in the efficiency of heat exchange due to formation ofwater droplets and deposition of fouling substances on cooling fins, forthe protection of building exterior walls and the like from fouling byimproving their property to eliminate (self-clean), with rain or water,fouling (airborne hydrophobic substances) deposited on the buildingexterior walls, for the improvement of dew preventing property ofbuilding interior finish paints and materials and the like, for theimprovement of contact lens wear comfort and anti-fouling property, andfor water-retention materials used for the greening of deserts or thegrowth promotion of general plants.

In these applications, the products are large in size or complex instructure, accuracy is required, productivity, controllability andproduct flexibility and safety are needed, water absorbency is needed,and coloration or dyeing is preferred. Accordingly, difficulties areencountered with inorganic materials in any instances, resulting in anincreasingly high demand for organic materials.

Known as organic materials capable of showing high water wettabilityinclude polymers such as polyvinyl alcohol [water contact angle: 36°,“Cho-shinsui Cho-hassuika Gijutsu (Superhydrophilicity, SuperWater-repellancy Imparting Technology)”, Published by Gijutsu JohoKyokai Co., Ltd., 2001], polyisopropylacrylamide (water contact angle:about 44° Langmuir, 11, 2301, 1995), and polyacrylonitrile (watercontact angle: about 53°, Desalination, 72, 263, 1989).

These polymers show the effect by hydroxyl groups, nitrile groups oramide groups which they themselves have. These functional groups are,however, known to be high in reactivity, and in some instances, may tendto cause a quality deterioration or change in final products due toinduction of undesired unnecessary reactions such as acetylation withaldehydes, esterification with acids or acid anhydrides, changes intoamides or carboxylic acids through hydrolysis and esterification byalcoholysis or the like, and induction of Diels-Alder reaction orMichael addition [“Plastic Jiten (Plastic Dictionary)”, Published byAsakura-Shoten Pub., Co., Ltd., 1992]. Such polymers are accompanied byfurther problems such that they themselves may be dissolved or elutedinto water and may be low in mechanical strength or the like.

With a view to solving, for example, problems of dissolution or elution,mechanical strength and the like, it has been proposed to addcopolymerizable compounds to form them into network polymers. Thismodification, however, has a tendency of deteriorating the wettability,and is not considered to be a proposal that assures sufficient strengthwhile retaining high wettability.

As an unconventional material, an agar gel (water contact angle: about20°, Langmuir, 10, 2435, 1994) is known. It is, however, not consideredto be sufficient in physical and chemical properties for itsinsufficient mechanical strength, insufficient heat resistance andinsufficient water resistance and chemical resistance. Practically, itis extremely difficult to use it for such purposes as described above.

As other methods for exhibiting high water wettability, methods whichprimarily involve surface modifications are known, including a methodthat provides a photocatalytic reaction layer of titanium oxide (JP11-58629 A, JP 11-1659 A), a method that coats a coating formulationmaking use of silanol groups (JP 9-40907 A, JP 9-40908 A, JP 11-21826A), a method that subsequent to corona discharge treatment, provides alayer containing silyl groups and ionic hydrophilic groups (carboxylgroups) and polyvinyl alcohol (JP 9-76428 A), a method that provides alayer making use of a quaternary ammonium base (JP 10-296895 A), amethod that forms a number of micropits on a surface by etchingtreatment (JP 7-198290 A), a method that introduces active hydrogengroups such as an amido group, carboxyl group and hydroxyl group, orionic functional groups such as sodium sulfonate, into a surface bygraft copolymerization (J. Poly. Sci., Part A: Polym. Chem., 32, 1569,1994; Macromolecules, 25, 6842, 1992), and a method that treats asurface with a chloric acid-potassium chlorate mixed solution [Polymer(Korea), 24, 877, 2000].

According to these methods, high water wettability can be certainlyrealized in some instances. However, they tend to cause various problemssuch as decomposition at the interface with a coated material through aphotocatalytic reaction, ineffectiveness in a dark ambient, delaminationdue to differences in a physical property such as coefficient of linearexpansion, flexibility or refractive index, crazing in a coating layeror a coated material, development of interference bands, insufficientstrength and weather resistance of a coating layer and a treatedsurface, and a reduction in performance due to an undesired reactionwith active hydrogen groups or ionic groups. On top of these problems,these methods generally require high ingenuity and special apparatus inmany instances, and also require a procedure of forming molded orotherwise formed products beforehand and then treating or coating theproducts further. These surface-modifying methods, therefore, areproposals that lead to cumbersome production and are not considered tobe effective, tend to result in high cost, and in some instances, alsohave some doubts in safety.

In the field of resins, polymers and the like, on the other hand, thepossession of excellent transparency is significantly effective. Theycan be used in the field of optical materials led by spectacle lenses,contact lenses, camera lenses, pickup lenses and organic glasses and thefield of transparent materials such as transparent films, and moreover,are expected to develop new markets and high functionality, such asimprovements in color vividness and luster, in the field of paints,coating formulations and the like.

Nonetheless, it has been unknown whether or not high-wettability organicpolymers with which the present invention are concerned have hightransparency.

DISCLOSURE OF THE INVENTION

Namely, it has been extremely difficult to solve the above-mentionednumerous problems and to propose organic polymers, resins and the likehaving high wettability and high transparency.

With such circumstances in view, the present inventors have proceededwith an extensive investigation. As a result, it has been found that useof a polymerizable compound having a polar structure, the dipolar momentof which is high (about 3 debyes or higher), as a partial structure iseffective for solving the problems and also that among such polarstructures, an alkylene(thio)urea structure analogous to the structureof polyurea considered to be poor in practical utility for its high costand low thermal stability [“Plastic Daijiten (Encyclopedia ofPlastics)”, Published by Kogyo Chosakai Publishing Co., Ltd.] is moreeffective. The present inventors have also found polymerizable compoundshaving a novel alkylene(thio)urea structure which can bring about morepreferred results.

The present inventors have also found that the wettability of a polymeris drastically improved by copolymerizing a polymerizable compoundhaving the above-described polar structure.

According to the above method, organic polymers which are physically andchemically stable despite their high water wettability and are excellentin transparency can be efficiently obtained without needing specialingenuity and apparatus and a cumbersome procedure such as conversion.organic polymers according to the present invention can be suitably usedfor applications in antifouling materials (self-cleaning materials),anti-mist materials, dew preventing materials, water (liquid) absorbentmaterials, optical materials and the like. Described specifically, thepresent invention relates to:

[3] An organic polymer as defined in [1] or [2], which has a polarstructure of 3 debyes or higher in dipole moment.

[4] A molded or otherwise formed product comprising an organic polymeras defined in [1], [2] or [3].

[5] A polymerizable compound comprising, in a molecule thereof, one ormore of the following partial structural formula (A):

wherein A₁ to A₆ each independently represent a hydrogen atom or analkyl group having 1 to 6 carbon atoms, X₁ represents O or S, and 1stands for an integer of 0 to 2, and one or more thioepoxy groups,allylthio-carbonyl groups or allyloxycarbonyl groups.

[6] A polymerizable compound comprising, in a molecule thereof, one ormore of the following partial structural formula (A):

wherein A₁ to A₆ each independently represent a hydrogen atom or analkyl group having 1 to 6 carbon atoms, X₁ represents O or S, and lstands for an integer of 0 to 2, and two or more mercapto groups,glycidylthio groups or (meth)acryloylthio groups.

[7] A polymerizable compound represented by the following formula (B):

wherein A₁ to A₆ each independently represent a hydrogen atom or analkyl group having 1 to 6 carbon atoms, X₁ represents O or S, 1 standsfor an integer of 0 to 2, R₁ to R₄ each independently represent ahydrogen atom, a hydroxy group, a mercapto group, an alkyl group having1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, analkylthio group having 1 to 6 carbon atoms, or the below-describedformulas (C) to (F), m and n each independently stand for an integer offrom 0 to 10, M and N each independently stand for an integer of from 1to 10, R₅ and R₆ each independently represent an alkoxy group having 1to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, or thebelow-described formulas (C) to (F), with a proviso that any one or moreof R₁ to R₄ are any of the below-described formulas (C) to (E):

wherein A₇ represents a hydrogen atom or a methyl group, and X₂represents O or S;

wherein A₈ represents a hydrogen atom or a methyl group, and X₃ and X₄each independently represent O or S; and

wherein A₁ to A₆ each independently represent a hydrogen atom or analkyl group having 1 to 6 carbon atoms, X₁ or X₅ represents O or S, lstands for an integer of 0 to 2, R₇ each independently represents ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkylgroup having 2 to 12 carbon atoms or an alkylthioalkyl group having 2 to12 carbon atoms, R₈ and R₉ each independently represent a hydrogen atom,a hydroxy group, a mercapto group, an alkyl group having 1 to 6 carbonatoms, an alkoxy group having 1 to 6 carbon atoms or an alkylthio grouphaving 1 to 6 carbon atoms, q stands for an integer of from 1 to 6, andr stands for an integer of an integer of from 0 to 3.

[8] A polymerizable composition comprising a polymerizable compound asdefined in [5], [6] or [7].

[9] An organic polymer available from polymerization of a polymerizablecompound as defined in [5], [6] or [7] or a polymerizable composition asdefined [8] and having a water contact angle of 20° or smaller.

[10] An organic polymer available from polymerization of a polymerizablecompound as defined in [5], [6] or [7] or a polymerizable composition asdefined in [8] and having a water contact angle of 7° or smaller.

[11] A molded or otherwise formed product comprising an organic polymeras defined in [8] or [9].

[12] Use, as an antifouling material, of an organic polymer as definedin [1], [2], [3], [9] or [10] or a molded or otherwise formed product asdefined in [4] or [11].

[13] Use, as an anti-mist material, of an organic polymer as defined in[1], [2], [3], [9]or [10] or a molded or otherwise formed product asdefined in [4] or [11].

[14] Use, as a dew preventing material, of an organic polymer as definedin [1], [2], [3], [9] or [10] or a molded or otherwise formed product asdefined in [4] or [11].

[15] Use, as a water(liquid) absorbent material, of an organic polymeras defined in [1], [2], [3], [9] or [10] or a molded or otherwise formedproduct as defined in [4] or [11].

[16] Use, as an optical material, of an organic polymer as defined in[1], [2], [3], [9] or [10] or a molded or otherwise formed product asdefined in [4] or [11].

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a ¹H-NMR chart of chloroethyloxazolidone obtained in Example1;

FIG. 2 is a ¹³C-NMR chart of chloroethyloxazolidone obtained in Example1;

FIG. 3 is a ¹H-NMR chart of N-methoxyethyl-N′-hydroxyethyl-ethyleneureaobtained in Example 1;

FIG. 4 is a ¹³C-NMR chart of N-methoxyethyl-N′-hydroxyethyl-ethyleneureaobtained in Example 1;

FIG. 5 is a ¹H-NMR chart of N-methoxyethyl-N′-mercaptoethyl-ethyleneureaobtained in Example 2;

FIG. 6 is an IR chart of N-methoxyethyl-N′-mercaptoethyl-ethyleneureaobtained in Example 2;

FIG. 7 is a ¹H-NMR chart of N,N′-bis(hydroxyethyl)-ethyleneurea obtainedin Example 3;

FIG. 8 is a ¹³C-NMR chart of N,N′-bis(hydroxyethyl)-ethyleneureaobtained in Example 3;

FIG. 9 is a ¹H-NMR chart of N,N′-bis(mercaptoethyl)-ethyleneureaobtained in Example 3;

FIG. 10 is a ¹³C-NMR chart of N,N′-bis(mercapto-ethyl)-ethyleneureaobtained in Example 3;

FIG. 11 is a ¹H-NMR chart ofN-methoxyethyl-N′-methacryloyloxyethyl-ethyleneurea obtained in Example4;

FIG. 12 is a ¹³C-NMR chart ofN-methoxyethylN′-methacryloyloxyethyl-ethyleneurea obtained in Example4;

FIG. 13 is a ¹H-NMR chart ofN-methoxyethyl-N′-acryloylthioethyl-ethyleneurea obtained in Example 5;

FIG. 14 is an IR chart ofN-methoxyethyl-N′-acryloylthioethyl-ethyleneurea obtained in Example 5;

FIG. 15 is a ¹H-NMR chart ofN-methoxyethyl-N′-allylthiocarbonatoethyl-ethleneurea obtained inExample 6;

FIG. 16 is a ¹³C-NMR chart ofN-methoxyethylN′-allylthiocarbonatoethyl-ethyleneurea obtained inExample 6;

FIG. 17 is a ¹H-NMR chart ofN-methoxyethyl-N′-allylcarbonatoethyl-ethyleneurea obtained in Example7;

FIG. 18 is a ¹³C-NMR chart ofN-methoxyethylN′-allylcarbonatoethyl-ethyleneurea obtained in Example 7;

FIG. 19 is a ¹H-NMR chart ofN-methoxyethyl-N′-glycidyloxyethyl-ethyleneurea obtained in Example 8;

FIG. 20 is an IR chart ofN-methoxyethyl-N′-glycidyloxyethyl-ethyleneurea obtained in Example 8;

FIG. 21 is a ¹H-NMR chart ofN,N′-bis(methacryloyl-oxyethyl)-ethyleneurea obtained in Example 9;

FIG. 22 is a ¹³C-NMR chart ofN,N′-bis(methacryloyl-oxyethyl)-ethyleneurea obtained in Example 9;

FIG. 23 is a ¹H-NMR chart of N,N′-bis(allyl-carbonatoethyl)-ethyleneureaobtained in Example 10;

FIG. 24 is a ¹³C-NMR chart ofN,N′-bis(allyl-carbonatoethyl)-ethyleneurea obtained in Example 10;

FIG. 25 is a ¹H-NMR chart of N,N′-bis(acryloylthio-ethyl)-ethyleneureaobtained in Example 11;

FIG. 26 is a ¹³C-NMR chart of N,N′-bis(acryloylthio-ethyl)-ethyleneureaobtained in Example 11;

FIG. 27 is a ¹H-NMR chart ofN,N′-bis(allylthio-carbonatoethyl)-ethyleneurea obtained in Example 12;

FIG. 28 is a ¹³C-NMR chart ofN,N′-bis(allylthio-carbonatoethyl)-ethyleneurea obtained in Example 12;

FIG. 29 is a ¹H-NMR chart of N,N′-bis(glycidylthio-ethyl)-ethyleneureaobtained in Example 13;

FIG. 30 is a ¹³C-NMR chart of N,N′-bis(glycidylthio-ethyl)-ethyleneureaobtained in Example 13;

FIG. 31 is a ¹H-NMR chart ofN,N′-bis(methacryloyl-oxymethyl)-ethyleneurea obtained in Example 14;

FIG. 32 is a ¹³C-NMR chart ofN,N′-bis(methacryloyl-oxymethyl)-ethyleneurea obtained in Example 14;

FIG. 33 is a ¹H-NMR chart of N,N′-bis(glycidyloxy-ethyl)-ethyleneureaobtained in Example 15;

FIG. 34 is an IR chart of N,N′-bis(glycidyloxy-ethyl)-ethyleneureaobtained in Example 15;

FIG. 35 is a ¹H-NMR chart ofN,N′-bis(thioglycidyl-thioethyl)-ethyleneurea obtained in Example 16;

FIG. 36 is a ¹³C-NMR chart ofN,N′-bis(thioglycidyl-thioethyl)-ethyleneurea obtained in Example 16;

FIG. 37 is a ¹H-NMR chart ofN,N′-bis(2-hydroxy-3-acryloyloxy-propyl)-ethyleneurea obtained inExample 17;

FIG. 38 is an IR chart ofN,N′-bis(2-hydroxy-3-acryloyloxy-propyl)-ethyleneurea obtained inExample 17;

FIG. 39 is a ¹H-NMR chart ofN,N′-bis{6-(N-methyl-imidazolidinonyl-N′-)-2-(methacryloyloxy)-4-thiahexyl}-ethyleneureaobtained in Example 18;

FIG. 40 is a ¹³C-NMR chart ofN,N′-bis{6-(N-methyl-imidazolidinonyl-N′-)-2-(methacryloyloxy)-4-thiahexyl}-ethyleneureaobtained in Example 18;

FIG. 41 is a ¹H-NMR chart of N,N′-bis(acryloyloxy-ethyl)-ethyleneureaobtained in Example 19;

FIG. 42 is a ¹³C-NMR chart of N,N′-bis(acryloyloxy-ethyl)-ethyleneureaobtained in Example 19;

FIG. 43 is a ¹H-NMR chart ofN,N′-bis{2-mercapto-methyl-2-(2-mercaptoethylthio)-ethyl}-ethyleneureaobtained in Example 20;

FIG. 44 is a ¹³C-NMR chart ofN,N′-bis{2-mercapto-methyl-2-(2-mercaptoethylthio)-ethyl}-ethyleneureaobtained in Example 20;

FIG. 45 is a ¹H-NMR chart of N,N′-diallyl-ethyleneurea obtained inExample 21;

FIG. 46 is an MS spectrum of N,N′-diallyl-ethyleneurea obtained inExample 21;

FIG. 47 is a ¹H-NMR chart of N-mono(allyloxy-carbonyl)-ethyleneureaobtained in Example 22;

FIG. 48 is an MS spectrum of N-mono(allyloxy-carbonyl)-ethyleneureaobtained in Example 22;

FIG. 49 is a ¹H-NMR chart of N,N′-di(allyloxy-carbonyl)-ethyleneureaobtained in Example 23;

FIG. 50 is an MS spectrum of N,N′-di(allyloxy-carbonyl)-ethyleneureaobtained in Example 23;

FIG. 51 is a ¹H-NMR chart of N-mono(methacryloyl)-ethyleneurea obtainedin Example 24;

FIG. 52 is an MS spectrum of N-mono(methacryloyl)-ethyleneurea obtainedin Example 24;

FIG. 53 is a ¹H-NMR chart of N,N′-di(methacryloyl)-ethyleneurea obtainedin Example 25;

FIG. 54 is an MS spectrum of N,N′-di(methacryloyl)-ethyleneurea obtainedin Example 25;

FIG. 55 is a ¹H-NMR chart of N-methyl-N′-glycidyl-ethyleneurea obtainedin Example 26;

FIG. 56 is an MS spectrum of N-methyl-N′-glycidyl-ethyleneurea obtainedin Example 26;

FIG. 57 is a ¹H-NMR chart of N-methyl-N′-acryloyl-oxyethyl-ethyleneureaobtained in Example 27;

FIG. 58 is a ¹H-NMR chart of N-acryloyl-oxazolidone obtained in Example28;

FIG. 59 is an MS spectrum of N-acryloyl-oxazolidone obtained in Example28;

FIG. 60 is a ¹H-NMR chart of N-allyl-oxazolidone obtained in Example 29;

FIG. 61 is an MS spectrum of N-allyl-oxazolidone obtained in Example 29;

FIG. 62 is an MS spectrum of N-vinyl-oxazolidone obtained in Example 30;

FIG. 63 is a ¹H-NMR chart of N-acryloyl-pyrrolidone obtained in Example31;

FIG. 64 is an MS spectrum of N-acryloyl-pyrrolidone obtained in Example31;

FIG. 65 is a ¹H-NMR chart of N-allyl-pyrrolidone obtained in Example 32;

FIG. 66 is an MS spectrum of N-allyl-pyrrolidone obtained in Example 32;

FIG. 67 is a ¹H-NMR chart of N-allyl-N-methyl-acetamide obtained inExample 33; and

FIG. 68 is an MS spectrum of N-allyl-N-methyl-acetamide obtained inExample 33.

BEST MODES FOR CARRYING OUT THE INVENTION

The present invention will hereinafter be described in detail.

The organic polymer having high water wettability, to which the presentinvention relates, has a water contact angle in a range of from 0 to20°, preferably in a range of from 0 to 7°. As the water contact anglebecomes smaller, antifouling property is improved further. Antifoulingproperty is substantially satisfactory when the water contact angle isabout 20° or smaller, and is fully satisfactory when the water contactangle is 10° or smaller. When the water contact angle is 7° or smaller,prevention of misting by steam or the like is also become feasible sothat the organic polymer is in a most preferred mode.

The molded or otherwise formed product according to the presentinvention is a molded or otherwise formed product which comprises anorganic polymer having a water contact angle of from 0 to 20° or anorganic polymer having a water contact angle of from 0 to 7°.Specifically, it can be, for example, a molded or otherwise formedproduct comprising only one organic polymer according to the presentinvention, or a conventional, molded or otherwise formed organic orinorganic product with a coating formulation, paint, laminatingmaterial, film or the like, which contains the organic polymer accordingto the present invention, cured, coated or adhered thereon.

These molded or otherwise molded products may optionally contain, inaddition to the organic polymer according to the present invention,other components, for example, stabilizers, colorants, fragrances,bactericides, binders, fillers, organic polymers other than those of thepresent invention, fillers, glass, metals, metal oxides, organometals,surfactants and the like, as needed depending on desired physicalproperties, characteristic properties, purposes, applications and thelike to extents not causing a problem.

The organic polymers according to the present invention arecharacterized in that they contain in their molecular structures polarstructures the dipolar moments of which are large. Among these, organicpolymers having polar structures of 3 debyes or greater are preferred,organic polymers having aprotic polar structures of 3 debyes or greaterare more preferred. Particularly effective are structures each of whichcontains one or more heteroatoms such as oxygen atom(s), nitrogenatom(s), phosphorus atom(s), sulfur atom(s) and/or the like.Illustrative are alkylene(thio)urea structures, oxazolidone structure,pyrrolidone structure, lactone structures, sulfone structures, sulfolanestructure, amide structures, alkyl(thio)urea structures, sulfonestructures, sulfoxide structures, piperazin-2,3-dione structure,acetyleneurea structure, caprolactam structures, alkylenecarbonatestructures, and phosphate ester structures. For example, aN,N′-dimethyl-ethyleneurea structure which is a sort ofalkylene(thio)urea structure is a structure that has high dipolar moment(4.1 debyes), is low in crystallinity and permits relatively easypolyfunctioning (bi- or higher functioning) effective for the retentionof mechanical strength and heat resistance.

It is also possible to significantly modify the properties of eachorganic polymer according to the present invention or to impart one ormore new functions to it by adding one or more other components.

One or more new functions can be easily imparted. For example, a highrefractive index can be imparted while retaining wettability,hydrophilicity, transparency and the like by newly adding apolymerizable compound, which contains one or more sulfur atoms, as acopolymerizable component. High adhesion property or the like can beimparted while retaining wettability, hydrophilicity, transparency andthe like by adding a polymerizable, active-hydrogen-containing componentsuch as (meth)acrylic acid. Further, by adding a metal such as silver orlithium, an organometal salt such as an alkaline metal (meth)acrylate,iodine, an iodonium salt, or the like, antimicrobial property can beimparted while retaining wettability and hydrophilicity althoughtransparency may be impaired in some instances.

A description will next be made about novel polymerizable compoundshaving alkylene(thio)urea structures of specific structures, which canreadily bring about preferred results in the organic polymers accordingto the present invention.

Described specifically, the novel polymerizable compounds according tothe present invention are the compounds described in [5], [6] and [7].

A₁ to A₆ in the partial structures of the formulas (A), (B) and (F)described in [5], [6] and [7] each independently represents a hydrogenor a linear (or branched) alkyl group having 1 to 6 carbon atoms. Fromthe standpoint of the viscosities and the like of the polymerizablecompounds and polymerizable compositions, hydrogen and linear (orbranched) alkyl groups having 1 to 3 carbon atoms are preferred, and insome instances, hydrogen and methyl group may be more preferred. A₁ toA₆ do no contain any cyclic structure such as an aromatic ring, andfurther, any two or more of them do not fuse together to form a ringstructure. In a form having a ring structure, the polymerizable compoundmay develop inconvenience in that it tends to crystallize by itself,leads to a higher viscosity, or has lower solubility. The alkyl grouphaving 1 to 6 carbon atoms may contain one or more heteroatoms such asoxygen atom(s), sulfur atom(s) and/or nitrogen atom(s) as needed to anextent not causing a problem, and its hydrogen atoms may be substitutedpartially or wholly by a like number of halogen atoms such as fluorineatoms. Non-inclusion of any heteroatom is, however, desired forhemiacetal forms each of which is susceptible to hydrolysis when one ormore heteroatoms are contained.

X₁ to X₅ in the partial structural formulas (A) to (D) and (F) eachindependently represents O or S, and selection of one of theseheteroatoms can be made appropriately depending on the purpose. From thestandpoint of ease in synthesis and cost, O tends to be relativelypreferred.

l in the partial structural formulas (A), (B) and (F) stands for aninteger of from 0 to 2. Basically, no problem or inconvenience ariseswith any of 0 (5-membered ring), 1 (6-membered ring) and 2 (7-memberedring). From the standpoint of solubility, crystallinity, cost, ease insynthesis and the like, however, 0 or 1 is relatively preferred, and 0may be more preferred in some instances.

The partial structural formulas (A) and (B) may each independently bebonded with one or more of polymerizable functional groups {thioepoxygroups, allylthiocarbonyl groups, allyloxycarbonyl groups, mercaptogroups, glycidylthio groups, (meth)acryloylthio groups, and the partialstructures (C) to (E)}. From the standpoint of cost, ease in synthesisand the like, it is preferred to contain 1 to 6 of these polymerizablefunctional groups bonded in a molecule, and in some instances, bondingof 1 to 4 of them may be more preferred.

Among these polymerizable functional groups, (meth)acryloylthio group,allylthiocarbonyl group, allyloxycarbonyl group, the partial structuralformula (C) and the partial structural formula (D) are relativelypreferred from the standpoint of photopolymerization reactivity level,and (meth)acryloylthio group and partial structural formula (C) tend tobe more preferred.

From the standpoint of thermopolymerization reactivity level, on theother hand, mercapto group, thioepoxy group, (meth)acryloylthio group,allylthio-carbonyl group, allyloxycarbonyl group, the partial structuralformula (C) and the partial structural formula (D) are relativelypreferred.

The polymerizable functional group of the partial structural formula (E)in the present invention tends to be relatively low in polymerizationreactivity.

When the novel polymerizable compounds according to the presentinvention contain a bond chain or the like in addition to polymerizablefunctional group(s) bonded to the partial structural formula (A) or thepartial structural formula (B), preferred examples of the partialstructural formula can be covalently bonding organic chains such asalkylene, alkylenoxy, poly(alkylenoxy), alkylenethio,poly(alkylenethio), fluoroalkylene, cycloalkylene, arylene andarylalkylene. From the standpoint of solubility, transparency, weatherresistance, easy in synthesis, and the like, alkylene, alkylenoxy,poly(alkylenoxy), alkylenethio, poly(alkylenethio) and the like arerelatively preferred.

They can be contained either singly or in combination, and can be eitherlinear or branched. It is, however, to be borne in mind that the presentinvention is not limited only to these bonding organic chains.

In the case of a polymerizable compound containing the partialstructural formula (B) and the partial structural formula (F), theseformulas are independent from each other. When the partial structuralformula (B) is a 5-membered ring, for example, the partial structuralformula (F) is not required to be a 5-membered ring but can also beeither a 6-membered ring, 7-membered ring or the like without developingany problem or inconvenience.

R₁ to R₄ in the partial structural formula (B) each independentlyrepresents a hydrogen atom, a hydroxyl group, a mercapto group, an alkylgroup having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbonatoms, an alkylthio group having 1 to 6 carbon atoms, or any one of thepartial structural formulas (C) to (F).

The alkyl, alkoxy and alkylthio groups, each of which has 1 to 6 carbonatoms, can independently be either linear or branched. From thestandpoint of the viscosities or the like of the polymerizable compoundand polymerizable composition, a carbon number in a range of from 1 to 3is preferred.

Further, the alkyl, alkoxy and alkylthio groups, each of which has 1 to6 carbon atoms, may each contain one or more heteroatoms such as oxygenatoms, sulfur atoms and nitrogen atoms. Their hydrogen atoms may besubstituted partially or wholly by a like number of halogen atoms suchas fluorine atoms. Non-inclusion of any heteroatom is, however, desiredfor hemiacetal forms each of which is susceptible to hydrolysis when oneor more heteroatoms are contained.

In the partial structural formula (B), m and n each independently standfor an integer of form 0 to 10, with 1 to 6 being relatively preferredand 1 to 3 being more preferred.

Similarly, M and N each independently stand for an integer of from 1 to10, with 1 to 3 being relatively preferred and 1 to 2 being morepreferred.

A₇ and A₈ in the partial structural formulas (C) to (E) representhydrogen or a methyl group, and the hydrogen atoms may be substitutedpartially or wholly by a like number of halogen atoms such as fluorineatoms as needed to an extent not causing a problem.

In the formula (F), R₇ each independently represents a hydrogen atom, analkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to12 carbon atoms, or an alkylthioalkyl group having 2 to 12 carbon atoms,and R₈ and R₉ each independently represent a hydrogen atom, a hydroxygroup, a mercapto group, an alkyl group having 1 to 6 carbon atoms, analkoxy group having 1 to 6 carbon atoms, or an alkylthio group.

When R₇ in the formula (F) is an alkyl group having 1 to 6 carbon atomor an alkoxyalkyl or alkylthioalkyl group having 2 to 12 carbon atoms,these groups may independently be linear or branched. From thestandpoint of the viscosities or the like of the polymerizable compoundand polymerizable composition, a carbon number in a range of from 1 to 3may be preferred in some instances.

When one or each of R₈ and R₉ in the formula (F) is an alkyl, alkoxy oraralkylthio group having 1-6 carbon atoms, the group can be eitherlinear or branched. Its carbon number may preferably be in a range offrom 1 to 3 in some instances.

R₇ to R₉ in the formula (F) may contain one or more heteroatoms such asoxygen atoms, sulfur atoms or nitrogen atoms as needed to an extent notcausing a problem. The hydrogen atoms may be substituted partially orwholly with a like number of halogen atoms such as fluorine atoms.Non-inclusion of any heteroatom is, however, desired for hemiacetalforms each of which is susceptible to hydrolysis when one or moreheteroatoms are contained.

In the formula (F), q stands for an integer of from 1 to 6 and r standsfor an integer of an integer of from 0 to 3. From ease in synthesis, acombination of 2 to 3 as q and 1 as r is relatively preferred.

In each of the novel polymerizable compounds according to the presentinvention, the hydrogen atoms which make up the compound may besubstituted partially or wholly with halogen atoms such as fluorineatoms as needed to an extent not causing a problem as appreciated fromthe foregoing.

As described above, the novel polymerizable compounds according to thepresent invention have been described in detail. To facilitate theunderstanding further, certain representative polymerizable compoundswill be exemplified below. It should, however, be borne in mind that thepresent invention shall not be limited only to the compounds to beexemplified. For example, the compounds shown in the below-describedtable can be mentioned. In the table, each compound corresponds to bothof the structural formula described before the table.

R7, R7′ (not in order) Methylthio- m,n/r,r′ ethyl, (not in Methyl,Methyl, Methyl, Methyl, Methoxyethyl, Methoxyethyl, Methoxyethyl,methylthio- order) methyl methyl methyl methyl methyl methoxyethylmethoxyethyl ethyl

2,2,/2,2 G3 Hydroxy Mercapto Hydroxymethyl Mercaptomethyl MercaptomethylMercaptomethyl Hydroxy Mercapto G4 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Allylthio- Glycidyl Glycidyl oxy thio oxymethyl thiomethylcarbonyl carbonyl oxy thio thiomethyl thiomethyl 2,2,/2,2 G3 HydroxyMercapto Hydroxymethyl Mercaptomethyl Mercaptomethyl Mercapto MercaptoHydroxy G4 Methacryloyl Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Allylthio- Allylthio- oxy thio oxymethylthiomethyl thiomethyl carbonyl carbonyl carbonyl thio thio oxy 2,2,/2,2G3 Hydroxy Hydroxymethyl Mercapto Mercaptomethyl MercaptomethylHydroxymethyl Hydroxymethyl Hydroxy- methyl G4 Allyloxy AllyloxyAllyloxy Allyloxy Acryloyl Methacryloyl Allyloxy Allylthio- carbonylcarbonyl carbonyl carbonyl thiomethyl oxymethyl carbonyl carbonyl oxyoxymethyl thio thiomethyl oxymethyl oxymethyl 2,2,/2,2 G3 HydroxyHydroxymethyl Mercapto Mercaptomethyl Hydroxymethyl HydroxymethylMercapto Hydroxy G4 Allylthio- Allylthio- Allylthio- Allylthio-Thioglycidyl Acryloyl Methacryloyl Allyloxy carbonyl carbonyl carbonylcarbonyl thiomethyl oxymethyl thio carbonyl oxy oxymethyl thiothiomethyl oxy 2,2,/2,2 G3 Hydroxy Mercapto Hydroxymethyl MercaptomethylHydroxymethyl Mercaptomethyl Mercapto Hydroxy G4 Glycidyl GlycidylGlycidyl Glycidyl Thioglycidyl Glycidyl Acryloyl Methacryloyl oxy thiooxymethyl thiomethyl oxymethyl thiomethyl thio oxy 2,2,/2,2 G3 HydroxyHydroxy Hydroxymethyl Hydroxymethyl Hydroxymethyl Hydroxy HydroxyHydroxy G4 Thioglycidyl Thioglycidyl Thioglycidyl Thioglycidyl GlycidylThioglycidyl Thioglycidyl Acryloyl oxy thio oxymethyl thiomethyloxymethyl thio oxy oxy 2,2,/2,2 G3 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Methacryloyl Methacryloyl Acryloyl oxy thio oxymethylthiomethyl carbonyl thiomethyl oxy oxy oxymethyl G4 Acryloyl AcryloylAcryloyl Acryloyl Allyloxy Methacryloyl Methacryloyl Acryloyl oxy thiooxymethyl thiomethyl carbonyl thiomethyl oxy oxy oxymethyl 2,2,/1,1 G3Methacryloyl Methacryloyl Methacryloyl Methacryloyl AllyloxyMethacryloyl Acryloyl Allyloxy oxy thio oxymethyl thiomethyl carbonyloxy thio thio carbonyl thio G4 Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Methacryloyl Acryloyl Allyloxy oxy thio oxythiomethyl carbonyl thio thio carbonyl methyl oxy thio 2,2,/1,1 G3Allyloxy Allyloxy Allyloxy Allyloxy Methacryloyl Acryloyl AllyloxyGlycidyl carbonyl carbonyl carbonyl carbonyl oxymethyl oxymethylcarbonyl oxymethyl oxy oxymethyl thio thiomethyl thiomethyl G4 AllyloxyAllyloxy Allyloxy Allyloxy Methacryloyl Acryloyl Allyloxy Glycidylcarbonyl carbonyl carbonyl carbonyl oxymethyl oxymethyl carbonyloxymethyl oxy oxymethyl thio thiomethyl thiomethyl 2,2,/1,1 G3Allylthio- Allylthio- Allylthio- Allylthio- Acryloyl Glycidyl GlycidylThioglycidyl carbonyl carbonyl carbonyl carbonyl thiomethyl oxythiomethyl thio oxy oxymethyl thio thiomethyl G4 Allylthio- Allylthio-Allylthio- Allylthio- Acryloyl Glycidyl Glycidyl Thioglycidyl carbonylcarbonyl carbonyl carbonyl thiomethyl oxy thiomethyl thio oxy oxymethylthio thiomethyl 2,2,/1,1 G3 Glycidyl Glycidyl Glycidyl GlycidylAllylthio- Allylthio- Allylthio- Allylthio- oxy thio oxymethylthiomethyl carbonyl carbonyl carbonyl carbonyl thiomethyl oxy thiooxymethyl G4 Glycidyl Glycidyl Glycidyl Glycidyl Allylthio- Allylthio-Allylthio- Allylthio- oxy thio oxymethyl thiomethyl carbonyl carbonylcarbonyl carbonyl thiomethyl oxy thio oxymethyl 2,2,/1,1 G3 ThioglycidylThioglycidyl Thioglycidyl Thioglycidyl Glycidyl ThioglycidylThioglycidyl Thioglycidyl oxy thio oxymethyl thiomethyl thio oxythiomethyl oxymethyl G4 Thioglycidyl Thioglycidyl ThioglycidylThioglycidyl Glycidyl Thioglycidyl Thioglycidyl Thioglycidyl oxy thiooxymethyl thiomethyl thio oxy thiomethyl oxymethyl

2,2,/2,2 G3 Hydroxy Mercapto Hydroxymethyl Mercaptomethyl MercaptomethylMercaptomethyl Hydroxy Mercapto G4 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Allylthio- Glycidyl Glycidyl oxy thio oxymethyl thiomethylcarbonyl carbonyl oxy thio thiomethyl thiomethyl 2,2,/2,2 G3 HydroxyMercapto Hydroxymethyl Mercaptomethyl Mercaptomethyl Mercapto MercaptoHydroxy G4 Methacryloyl Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Allylthio- Allylthio- oxy thio oxymethylthiomethyl thiomethyl carbonyl carbonyl carbonyl thio thio oxy 2,2,/2,2G3 Hydroxy Hydroxymethyl Mercapto Mercaptomethyl MercaptomethylHydroxymethyl Hydroxymethyl Hydroxy- methyl G4 Allyloxy AllyloxyAllyloxy Allyloxy Acryloyl Methacryloyl Allyloxy Allylthio- carbonylcarbonyl carbonyl carbonyl thiomethyl oxymethyl carbonyl carbonyl oxyoxymethyl thio thiomethyl oxymethyl oxymethyl 2,2,/2,2 G3 HydroxyHydroxymethyl Mercapto Mercaptomethyl Hydroxymethyl HydroxymethylMercapto Hydroxy G4 Allylthio- Allylthio- Allylthio- Allylthio-Thioglycidyl Acryloyl Methacryloyl Allyloxy carbonyl carbonyl carbonylcarbonyl thiomethyl oxymethyl thio carbonyl oxy oxymethyl thiothiomethyl oxy 2,2,/2,2 G3 Hydroxy Mercapto Hydroxymethyl MercaptomethylHydroxymethyl Mercaptomethyl Mercapto Hydroxy G4 Glycidyl GlycidylGlycidyl Glycidyl Thioglycidyl Glycidyl Acryloyl Methacryloyl oxy thiooxymethyl thiomethyl oxymethyl thiomethyl thio oxy 2,2,/2,2 G3 HydroxyHydroxy Hydroxymethyl Hydroxymethyl Hydroxymethyl Hydroxy HydroxyHydroxy G4 Thioglycidyl Thioglycidyl Thioglycidyl Thioglycidyl GlycidylThioglycidyl Thioglycidyl Acryloyl oxy thio oxymethyl thiomethyloxymethyl thio oxy oxy 2,2,/2,2 G3 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Methacryloyl Methacryloyl Acryloyl oxy thio oxymethylthiomethyl carbonyl thiomethyl oxy oxy oxymethyl G4 Acryloyl AcryloylAcryloyl Acryloyl Allyloxy Methacryloyl Methacryloyl Acryloyl oxy thiooxymethyl thiomethyl carbonyl thiomethyl oxy oxy oxymethyl 2,2,/2,2 G3Methacryloyl Methacryloyl Methacryloyl Methacryloyl AllyloxyMethacryloyl Acryloyl Allyloxy oxy thio oxymethyl thiomethyl carbonylthio thio carbonyl oxy thio G4 Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Methacryloyl Acryloyl Allyloxy oxy thio oxymethylthiomethyl carbonyl thio thio carbonyl oxy thio 2,2,/2,2 G3 AllyloxyAllyloxy Allyloxy Allyloxy Methacryloyl Acryloyl Allyloxy Glycidylcarbonyl carbonyl carbonyl carbonyl oxymethyl oxymethyl carbonyloxymethyl oxy oxymethyl thio thiomethyl thiomethyl G4 Allyloxy AllyloxyAllyloxy Allyloxy Methacryloyl Acryloyl Allyloxy Glycidyl carbonylcarbonyl carbonyl carbonyl oxymethyl oxymethyl carbonyl oxymethyl oxyoxymethyl thio thiomethyl thiomethyl 2,2,/2,2 G3 Allylthio- Allylthio-Allylthio- Allylthio- Acryloyl Glycidyl Glycidyl Thioglycidyl carbonylcarbonyl carbonyl carbonyl thiomethyl oxy thiomethyl thio oxy oxymethylthio thiomethyl G4 Allylthio- Allylthio- Allylthio- Allylthio- AcryloylGlycidyl Glycidyl Thioglycidyl carbonyl carbonyl carbonyl carbonylthiomethyl oxy thiomethyl thio oxy oxymethyl thio thiomethyl 2,2,/2,2 G3Glycidyl Glycidyl Glycidyl Glycidyl Allylthio- Allylthio- Allylthio-Allylthio- oxy thio oxymethyl thiomethyl carbonyl carbonyl carbonylcarbonyl thiomethyl oxy thio oxymethyl G4 Glycidyl Gycidyl GlycidylGlycidyl Allylthio- Allylthio- Allylthio- Allylthio- oxy thio oxymethylthiomethyl carbonyl carbonyl carbonyl carbonyl thiomethyl oxy thiooxymethyl 2,2,/2,2 G3 Thioglycidyl Thioglycidyl ThioglycidylThioglycidyl Glycidyl Thioglycidyl Thioglycidyl Thioglycidyl oxy thiooxymethyl thiomethyl thio oxy thiomethyl oxymethyl G4 ThioglycidylThioglycidyl Thioglycidyl Thioglycidyl Glycidyl ThioglycidylThioglycidyl Thioglycidyl oxy thio oxymethyl thiomethyl thio oxythiomethyl oxymethyl

2,2,/1,1 G3 Hydroxy Mercapto Hydroxymethyl Mercaptomethyl MercaptomethylMercaptomethyl Hydroxy Mercapto G4 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Allylthio- Glycidyl Glycidyl oxy thio oxymethyl thiomethylcarbonyl carbonyl oxy thio thiomethyl thiomethyl 2,2,/1,1 G3 HydroxyMercapto Hydroxymethyl Mercaptomethyl Mercaptomethyl Mercapto MercaptoHydroxy G4 Methacryloyl Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Allylthio- Allylthio- oxy thio oxymethylthiomethyl thiomethyl carbonyl carbonyl carbonyl thio thio oxy 2,2,/1,1G3 Hydroxy Hydroxymethyl Mercapto Mercaptomethyl MercaptomethylHydroxymethyl Hydroxymethyl Hydroxy- methyl G4 Allyloxy AllyloxyAllyloxy Allyloxy Acryloyl Methacryloyl Allyloxy Allylthio- carbonylcarbonyl carbonyl carbonyl thiomethyl oxymethyl carbonyl carbonyl oxyoxymethyl thio thiomethyl oxymethyl oxymethyl 2,2,/1,1 G3 HydroxyHydroxymethyl Mercapto Mercaptomethyl Hydroxymethyl HydroxymethylMercapto Hydroxy G4 Allylthio- Allylthio- Allylthio- Allylthio-Thioglycidyl Acryloyl Methacryloyl Allyloxy carbonyl carbonyl carbonylcarbonyl thiomethyl oxymethyl thio carbonyl oxy oxymethyl thiothiomethyl oxy 2,2,/1,1 G3 Hydroxy Mercapto Hydroxymethyl MercaptomethylHydroxymethyl Mercaptomethyl Mercapto Hydroxy G4 Glycidyl GlycidylGlycidyl Glycidyl Thioglycidyl Glycidyl Acryloyl Methacryloyl oxy thiooxymethyl thiomethyl oxymethyl thiomethyl thio oxy 2,2,/1,1 G3 HydroxyHydroxy Hydroxymethyl Hydroxymethyl Hydroxymethyl Hydroxy HydroxyHydroxy G4 Thioglycidyl Thioglycidyl Thioglycidyl Thioglycidyl GlycidylThioglycidyl Thioglycidyl Acryloyl oxy thio oxymethyl thiomethyloxymethyl thio oxy oxy 2,2,/1,1 G3 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Methacryloyl Methacryloyl Acryloyl oxy thio oxymethylthiomethyl carbonyl thiomethyl oxy oxy oxymethyl G4 Acryloyl AcryloylAcryloyl Acryloyl Allyloxy Methacryloyl Methacryloyl Acryloyl oxy thiooxymethyl thiomethyl carbonyl thiomethyl oxy oxy oxymethyl 2,2,/1,1 G3Methacryloyl Methacryloyl Methacryloyl Methacryloyl AllyloxyMethacryloyl Acryloyl Allyloxy oxy thio oxymethyl thiomethyl carbonylthio thio carbonyl oxy thio G4 Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Methacryloyl Acryloyl Allyloxy oxy thio oxymethylthiomethyl carbonyl thio thio carbonyl oxy thio 2,2,/1,1 G3 AllyloxyAllyloxy Allyloxy Allyloxy Methacryloyl Acryloyl Allyloxy Glycidylcarbonyl carbonyl carbonyl carbonyl oxymethyl oxymethyl carbonyloxymethyl oxy oxymethyl thio thiomethyl thiomethyl G4 Allyloxy AllyloxyAllyloxy Allyloxy Methacryloyl Acryloyl Allyloxy Glycidyl carbonylcarbonyl carbonyl carbonyl oxymethyl oxymethyl carbonyl oxymethyl oxyoxymethyl thio thiomethyl thiomethyl 2,2,/1,1 G3 Allylthio- Allylthio-Allylthio- Allylthio- Acryloyl Glycidyl Glycidyl Thioglycidyl carbonylcarbonyl carbonyl carbonyl thiomethyl oxy thiomethyl thio oxy oxymethylthio thiomethyl G4 Allylthio- Allylthio- Allylthio- Allylthio- AcryloylGlycidyl Glycidyl Thioglycidyl carbonyl carbonyl carbonyl carbonylthiomethyl oxy thiomethyl thio oxy oxymethyl thio thiomethyl 2,2,/1,1 G3Glycidyl Glycidyl Glycidyl Glycidyl Allylthio- Allylthio- Allylthio-Allylthio- oxy thio oxymethyl thiomethyl carbonyl carbonyl carbonylcarbonyl thiomethyl oxy thio oxymethyl G4 Glycidyl Glycidyl GlycidylGlycidyl Allylthio- Allylthio- Allylthio- Allylthio- oxy thio oxymethylthiomethyl carbonyl carbonyl carbonyl carbonyl thiomethyl oxy thiooxymethyl 2,2,/1,1 G3 Thioglycidyl Thioglycidyl ThioglycidylThioglycidyl Glycidyl Thioglycidyl Thioglycidyl Thioglycidyl oxy thiooxy thiomethyl thio oxy thiomethyl oxy methyl methyl G4 ThioglycidylThioglycidyl Thioglycidyl Thioglycidyl Glycidyl ThioglycidylThioglycidyl Thioglycidyl oxy thio oxy thiomethyl thio oxy thiomethyloxy methyl methyl

2,2,/1,1 G3 Hydroxy Mercapto Hydroxymethyl Mercaptomethyl MercaptomethylMercaptomethyl Hydroxy Mercapto G4 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Allylthio- Glycidyl Glycidyl oxy thio oxymethyl thiomethylcarbonyl carbonyl oxy thio thiomethyl thiomethyl 2,2,/1,1 G3 HydroxyMercapto Hydroxymethyl Mercaptomethyl Mercaptomethyl Mercapto MercaptoHydroxy G4 Methacryloyl Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Allylthio- Allylthio- oxy thio oxymethylthiomethyl thiomethyl carbonyl carbonyl carbonyl thio thio oxy 2,2,/1,1G3 Hydroxy Hydroxymethyl Mercapto Mercaptomethyl MercaptomethylHydroxymethyl Hydroxymethyl Hydroxy- methyl G4 Allyloxy AllyloxyAllyloxy Allyloxy Acryloyl Methacryloyl Allyloxy Allylthio- carbonylcarbonyl carbonyl carbonyl thiomethyl oxymethyl carbonyl carbonyl oxyoxymethyl thio thiomethyl oxymethyl oxymethyl 2,2,/1,1 G3 HydroxyHydroxymethyl Mercapto Mercaptomethyl Hydroxymethyl HydroxymethylMercapto Hydroxy G4 Allylthio- Allylthio- Allylthio- Allylthio-Thioglycidyl Acryloyl Methacryloyl Allyloxy carbonyl carbonyl carbonylcarbonyl thiomethyl oxymethyl thio carbonyl oxy oxymethyl thiothiomethyl oxy 2,2,/1,1 G3 Hydroxy Mercapto Hydroxymethyl MercaptomethylHydroxymethyl Mercaptomethyl Mercapto Hydroxy G4 Glycidyl GlycidylGlycidyl Glycidyl Thioglycidyl Glycidyl Acryloyl Methacryloyl oxy thiooxymethyl thiomethyl oxy thiomethyl thio oxy methyl 2,2,/1,1 G3 HydroxyHydroxy Hydroxymethyl Hydroxymethyl Hydroxymethyl Hydroxy HydroxyHydroxy G4 Thioglycidyl Thioglycidyl Thioglycidyl Thioglycidyl GlycidylThioglycidyl Thioglycidyl Acryloyl oxy thio oxy thiomethyl oxymethylthio oxy oxy methyl 2,2,/1,1 G3 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Methacryloyl Methacryloyl Acryloyl oxy thio oxymethylthiomethyl carbonyl thiomethyl oxy oxy oxymethyl G4 Acryloyl AcryloylAcryloyl Acryloyl Allyloxy Methacryloyl Methacryloyl Acryloyl oxy thiooxymethyl thiomethyl carbonyl thiomethyl oxy oxy oxymethyl 2,2,/2,2 G3Hydroxy Mercapto Hydroxymethyl Mercaptomethyl MercaptomethylMercaptomethyl Hydroxy Mercapto G4 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Allylthio- Glycidyl Glycidyl oxy thio oxymethyl thiomethylcarbonyl carbonyl oxy thio thiomethyl thiomethyl 2,2,/2,2 G3 HydroxyMercapto Hydroxymethyl Mercaptomethyl Mercaptomethyl Mercapto MercaptoHydroxy G4 Methacryloyl Methacryloyl Methacryloyl MethacryloylMethacryloyl Allyloxy Allylthio- Allylthio- oxy thio oxymethylthiomethyl thiomethyl carbonyl carbonyl carbonyl thio thio oxy 2,2,/2,2G3 Hydroxy Hydroxymethyl Mercapto Mercaptomethyl MercaptomethylHydroxymethyl Hydroxymethyl Hydroxy- methyl G4 Allyloxy AllyloxyAllyloxy Allyloxy Acryloyl Methacryloyl Allyloxy Allylthio- carbonylcarbonyl carbonyl carbonyl thiomethyl oxymethyl carbonyl carbonyl oxyoxymethyl thio thiomethyl oxymethyl oxymethyl 2,2,/2,2 G3 HydroxyHydroxymethyl Mercapto Mercaptomethyl Hydroxymethyl HydroxymethylMercapto Hydroxy G4 Allylthio- Allylthio- Allylthio- Allylthio-Thioglycidyl Acryloyl Methacryloyl Allyloxy carbonyl carbonyl carbonylcarbonyl thiomethyl oxymethyl thio carbonyl oxy oxymethyl thiothiomethyl oxy 2,2,/2,2 G3 Hydroxy Mercapto Hydroxymethyl MercaptomethylHydroxymethyl Mercaptomethyl Mercapto Hydroxy G4 Glycidyl GlycidylGlycidyl Glycidyl Thioglycidyl Glycidyl Acryloyl Methacryloyl oxy thiooxymethyl thiomethyl oxymethyl thiomethyl thio oxy 2,2,/2,2 G3 HydroxyHydroxy Hydroxymethyl Hydroxymethyl Hydroxymethyl Hydroxy HydroxyHydroxy G4 Thioglycidyl Thioglycidyl Thioglycidyl Thioglycidyl GlycidylThioglycidyl Thioglycidyl Acryloyl oxy thio oxymethyl thiomethyloxymethyl thio oxy oxy 2,2,/2,2 G3 Acryloyl Acryloyl Acryloyl AcryloylAllyloxy Methacryloyl Methacryloyl Acryloyl oxy thio oxymethylthiomethyl carbonyl thiomethyl oxy oxy oxymethyl G4 Acryloyl AcryloylAcryloyl Acryloyl Allyloxy Methacryloyl Methacryloyl Acryloyl oxy thiooxymethyl thiomethyl carbonyl thiomethyl oxy oxy oxymethyl

To an extent not causing problem, the hydrogen atoms may be substitutedpartially or wholly by a like number of halogen atoms such as fluorineatoms. These polymerizable compounds can be used either singly or incombination.

The polymerizable compounds according to the present invention can besynthesized by using numerous general reactions such as those describedin series publications of organic chemistry such as “Methoden derOrganischen Chemie (1971, Vierte Auflage Herausgegeben von Eugen Muller)and “Shin Jikken Kagaku Koza (Handbook of Experimental Chemistry)”(1975, The Chemical Society of Japan).

A description will be made taking as examples such representative groupsof compounds as will be described hereinafter.

Routes, which proceed through substantially the same reaction, will beidentified by the same numeral.

Route (1) is an alkylating reaction of an amine or urea, and a processusing, for example, an alkyl halide, alkylene carbonate, alkylene oxide,hydroxyalkyl halide, hydroxyalkyl sulfonate or the like is in commonuse.

In addition to the alkylation of the amine or urea, an alkyl(thio)ureaor alkylamine may be synthesized by reacting an alkylamine or the liketo a (thio)carbonyl having an electron attracting group as typified by(thio)phosgene or to an alkane having an electron attracting group astypified by dichloroethane or ethanedibenzene sulfonate.

Incidentally, to conduct mercaptoalkylation, a process using, forexample, an alkylene dithiocarbonate, alkylene sulfide, mercaptoalkylhalide, mercaptoalkyl sulfonate or mercaptoalkylamine or the like, canbe used in addition to converting a hydroxyl group into a mercaptogroup.

With a view to improving selectivity, the reactant may be used with itshydroxyl group or mercapto group converted beforehand into a protectinggroup such as an acetyloxy group, benzoxy group, benzyloxy group,acetylthio group, benzothio group or benzylthio group, and subsequently,a deprotecting reaction such as hydrolysis or reduction may be conductedto synthesize the desired compound.

Route (2) is a reaction that subjects the alkylamine or alkyl(thio)urea,which has been synthesized by Route (1), to ring closure to form analkylene(thio)urea ring.

When the alkylamine is subjected to ring closure, the number ofring-forming members in the alkylene(thio)urea ring is determined by thelength of the alkylene group. The yield tends to drop when the length ofthe alkylene group is too short or too long. It is relatively preferredthat the carbon number of the substituted or unsubstituted methylenestructure which makes up the alkylene moiety is in a range of from 2 to4, with 2 to 3 being more preferred.

For this ring closure of the alkylamine, carbon dioxide, carbondisulfide, (thio)phosgene, an alkylene(arylene) carbonate, (thio)urea orthe like is generally employed.

In the process for subjecting the alkyl(thio)urea to ring closure, onthe other hand, an alkane having electron attracting groups as typifiedby 1,2-dichloroethane, 1,2-dibromoethane, 1,2-ethanedibenzene sulfonate(5-membered ring), 1,2-dibromopropane (5-membered ring),1,3-dibromopropane (6-membered ring), 1,4-diiodobutane (7-membered ring)or the like is generally used.

For the synthesis of N,N′-bis(hydroxyethyl)-ethyleneurea, for example,an illustrative usable process can be to react urea with theN,N′-bis(hydroxyethyl)ethylenediamine, which has been obtained by Route(1), such that the diamine is subjected to ring closure.

The temperature of the above-described ring closing reaction differsbetween a (thio)carbonyl having an electron attracting group as typifiedby (thio)phosgene or the like and simple (thio)urea or the like. Whenurea or the like is reacted, for example, the reaction temperature canbe approximately 0 to 300° C, preferably 100 to 250° C., more preferably150 to 230° C.

To synthesize a compound of the alkylenethiourea structure, thiourea isused in place of urea.

Route (3) is a route to synthesize an N-(2-halogenoethyl)-2-oxazolidoneby reacting a bis(2-halogenoethyl)amine hydrohalogenide with an alkalinemetal carbonate, alkaline metal hydrogencarbonate or the like.

Use of a bis(3-halogenopropyl)amine hydrohalogenide in this reactionprovides an N-(3-halogenopropyl)-oxazinan-2-one having a 6-membered ringstructure.

The temperature of this reaction can approximately be in a range of from20 to 100° C., and a reaction temperature of from 30 to 60° C. may bringabout preferred results in some instances.

Route (4) is a reaction to synthesize a target alkylene(thio)ureastructure by reacting an amine with a compound of a heterocyclicstructure obtained through Route (3), such as a 2-oxazolidone oroxazinan-2-one.

For example, when 2-hydroxyethylamine is reacted with anN-(2-halogenoetyl)-2-oxazolidone, N,N′-bis(2-hydroxyethyl)-ethyleneureais obtained; when an excess of 3-amino-1,2-propanediol is reacted,N-hydroxyethyl-N′-{2,3-bis(hydroxy)propyl}-ethyleneurea is obtained.

The temperatures in these reactions can be approximately 0 to 250° C.,preferably 30 to 200° C., more preferably 60 to 150° C.

As a representative alternative process making use of oxazolidone as astarting raw material other than the above-described process, there isalso known a process which comprises reacting a halogenoalkyl isocyanateor the like with an N-halogenoethyl-2-oxazolidone to synthesize anN-halogenoethyl-N′-halogenoalkyl(or aryl)-ethyleneurea which serves asan intermediate in the present invention (JP 41-14991 B).

Route (5) is a reaction to convert hydroxyl groups into mercapto groups.

In general, the hydroxyl groups are converted into electron attractinggroups such as halogens or sulfonates by using a reagent such as thionylchloride, sulfuryl chloride, phosphorus pentoxide, phosphorustribromide, hydrochloric acid, hydrobromic acid, hydroiodic acid,methane sulfonyl chloride, trifluoromethane sulfonyl chloride, benzenesulfonyl chloride or tosyl chloride.

A process is next used, for example, to react an alkaline metal sulfidesuch as sodium hydrosulfide, potassium hydrosulfide or sodium sulfide orto react thiourea to form an isothiuronium salt and then to hydrolyzethe isothiuronium salt; to react sodium thiosulfate or the like to forma Bunte salt and then to hydrolyze the Bunte salt; to react an alkalinemetal N,N-dialkyldithiocarbamate, followed by hydrolysis; to react analkaline metal O-alkyl dithiocarbonate, followed by hydrolysis; to reacta Grignard reagent and then sulfur, followed by final hydrolysis orreduction; or to once react a thiol to synthesize a sulfide and then tocleave the sulfide with an alkaline metal or the like.

Of these processes, the process, which goes through an isothiuroniumsalt, is used relatively preferably.

To synthesize N-mercaptoethyl-N′-{1,3-dimercapto-2-propyl}-ethyleneurea,for example, an illustrative process can comprise reacting phosphorustribromide with a liquid mixture ofN-hydroxyethyl-N′-{2,3-dihydroxy-propyl}-ethyleneurea, which has beenobtained through Route (4), and chlorobenzene at 50 to 132° C., addingthiourea and water to the resultingN-bromoethyl-N′-{2,3-dibromo-propyl}-ethyleneurea and reacting them at60° C. to under reflux (105° C.) to convert the ethyleneurea into anisothiuronium salt, and subsequent to cooling, adding 25% aqueousammonium or hydrazine hydrate and hydrolyzing the isothiuronium salt at40-80° C.

To convert the hydroxyl groups directly into mercapto groups, anillustrative process can comprise reacting thiourea in the presence of amineral acid such as hydrochloric acid to synthesize an isothiuroniumsalt and then hydrolyzing the isothiuronium salt; directly reactinghydrogen sulfide; or reacting phosphorus pentasulfide.

To similarly synthesizeN-mercaptoethyl-N′-{1,3-dimercapto-2-propyl}-ethyleneurea withoutconducting halogenation, for example, with phosphorus tribromide or thelike, an illustrative process can comprise adding thiourea, hydrochloricacid solution and a catalytic amount of concentrated sulfuric acid toN-hydroxyethyl-N′-{2,3-dihydroxy-propyl}-ethyleneura, reacting themthoroughly under reflux (100 to 110° C.), and subsequent to cooling,adding basic water such as 25% aqueous ammonium or hydrazine hydrate andconducting hydrolysis at 40 to 80° C.

Route (6) is a reaction to introduce epoxy groups. For the introductionof epoxy groups, it is a common practice to react an epihalohydrin withthe hydroxy derivative or the thiol derivative to form a halohydrinderivative and then to subject the halohydrin derivative to ring closurewith a base to achieve epoxidation. The addition reaction and thering-closing reaction may be conducted concurrently in a single step,although these reactions are generally conducted in two steps.

Known as an alternative process is to oxidize a corresponding olefin, astypified by allyl groups, directly with hydrogen peroxide, an organicperoxide, air or the like; or to halogenize the olefin in an aqueoussolution to synthesize a halohydrin and then to subject it to ringclosure with a base.

Route (7) is a reaction to introduce thioepoxy groups.

To convert epoxy groups into thioepoxy groups, for example, it is acommon practice to react an alkaline metal thiocyanate, such as sodiumthiocyanate or potassium thiocyanate, with the corresponding epoxygroups; to react a thiourea or the like with the corresponding epoxygroups; or to react an aryl (or alkyl) phosphinic acid sulfide with thecorresponding epoxy groups.

Among these reactions for converting epoxy groups into thioepoxy groups,relatively preferred is the process which comprises reacting an alkalinemetal thiocyanate such as sodium thiocyanate or potassium thiocyanatewith the corresponding epoxy groups or the process which comprisesreacting a thiourea with the corresponding epoxy groups.

As other processes, there are also a process in which, after an alkalinemetal thiocyanate or a thiourea is likewise reacted with a halohydrinderivative as an intermediate for epoxy groups, the reaction product issubjected to ring closure with a base and a process in which a sulfurhalide, an aryl (or alkyl) thiosulfenyl halide or thiocyanic acid halideis reacted with an olefin represented by the corresponding allyl group.

To synthesizeN-(thioglycidylthioethyl)-N′-{1,3-bis(thioglycidylthio)-2-propyl}-ethyleneurea,for example, there is the following process: Epichlorohydrin is dropwiseadded to a liquid mixture, which has been formed by adding a catalyticamount of triethylamine toN-mercaptoethyl-N′-{1,3-dimercapto-2-propyl}-ethyleneurea obtained in(5), and reacted at an internal temperature of from 10 to 40° C. toconvert the ethyleneurea into a halohydrin derivative, and caustic sodais likewise added dropwise and reacted at an internal temperature offrom 20 to 50° C. to obtainN-(glycidylthioethyl)-N′-{1,3-bis(glycidylthio)-2-propyl}-ethyleneureaas an epoxy derivative.

Thiourea is then added to a liquid mixture of the thus-obtainedN-(glycidylthioethyl)-N′-{1,3-bis(glycidylthio)-2-propyl}-ethyleneureaand methanol, followed by a reaction at 10 to 40° C.

Route (8) is a reaction to subject the (thio)epoxy groups to ringopening.

Described specifically, an active-hydrogen-containing compound such asan alcohol, thiol, carboxylic acid or primary or secondary amine isreacted with the (thio)epoxy groups to subject the (thio)epoxy groups toring opening so that the (thio)epoxy compound is converted into ahydroxy compound (mercapto compound).

Preferred results may be obtained in some instances when a general(thio)epoxy ring-opening catalyst—such as a tertiary amine, a quaternaryamine halogenide, a quaternary amine hydroxide, a phosphine, anorganometal salt, an alkaline metal, an alkaline metal hydroxide, analkaline metal carbonate, an alkaline metal hydrogencarbonate, analkaline metal trifurate, a metal halide, a metal oxide, a metalalkoxylate, a boron trifluoride ether complex, or other organic orinorganic acid—is added in the reaction.

Route (9) is a reaction to react an acid halide or halogenochloroformatecontaining a polymerizable unsaturated group, such as a (meth)acrylicacid halide or an allyl halogenoformate, is reacted.

When synthesis of a (thio)acrylate derivative is desired, for example,acrylic acid chloride is reacted to the hydroxyl groups (or mercaptogroups).

Usable as an alternative process can be a two-step process in which achloropropionic acid halide is once reacted to form a chloropropionate(thio)ester and a base such as a tertiary amine is then added to conductdehydrohalogenation such that a (thio)acrylate derivative is formed.

To synthesizeN-acryloyloxyethyl-N′-{2,3-bis(acryloyloxy)propyl}-ethyleneurea, forexample, there is a process that at 20 to 50° C., acrylic acid chlorideis added dropwise to and reacted withN-hydroxyethyl-N′-{2,3-dihydroxy-propyl}-ethyleneurea obtained throughRoute (4).

Upon synthesizing the thio(meth)acrylate derivative, the mercaptoderivative available through Route (5) is used as a starting rawmaterial. However, the two-step process described as an alternativeprocess is relatively preferred because Michael addition reaction of themercapto groups tends to occur.

This applies equally to the synthesis of an allyl carbonate or the likethrough Route (10). In place of a (meth)acrylic acid halide, allylchloroformate synthesized from allyl alcohol and phosgene or the like,or similarly, sec-butynyl chloroformate, vinyl chloroformate orisopropenyl chloroformate is reacted.

When a thiocarbonate derivative is desired, such a chloroformate isreacted with the thiol derivative, or phosgene is reacted withallylthiol, sec-butynylthiol, vinylthiol or isopropenylthiol to obtain athioformate derivative, which is then reacted with a hydroxy derivative.

Further, in the case of a dithiocarbonate, a thiol derivative is reactedwith a thiochloroformate are reacted, and in the case of atrithiocarbonate, a dithiochloroformate synthesized from thiophosgene isreacted with the thiol derivative.

The temperatures of these reactions may be approximately −50 to 200° C.,preferably −20 to 150° C., more preferably 0 to 100° C.

To synthesizeN-allylthiocarbonatoethyl-N′-{1,3-bis(allylthiocarbonato)-2-propyl}-ethyleneurea,for example, there is a process that at 10 to 30° C., ally chloroformateis added to a liquid mixture ofN-mercaptoethyl-N′-{1,3-dimercapto-2-propyl}-ethyleneurea, which hadbeen obtained through Route (5), triethylamine and toluene as a solventand is reacted with the ethyleneurea.

Concerning the alkylene(thio)urea structure in the present invention,some processes have already been described above as processes forsynthesizing compounds each of which can be formed into thealkylenethiourea structure. There are, for example, a process in whichthiourea, ethylenethiourea and thiophosgene are used in place of urea,ethyleneurea and phosgene, respectively, and also, a process in which asulfurizing agent such as hydrogen sulfide, boron sulfide, phosphoruspentasulfide or Lawesson's reagent-is reacted with the alkyleneureastructure.

When it is desired to form, as branched structures, the organic linkagesconnecting the alkylene(thio)urea structure and polymerizable functionalgroups in the present invention, a process making use of a branched rawmaterial is relatively easy.

To synthesizeN,N′-bis(3-methacryloyloxy-2,2-dimethyl-1-propyl)-4-methylimidazolidinone,for example, there is a process in which, after3-hydroxy-2,2-dimethylpropyl-1-bromide is reacted with1,2-diaminopropane, the reaction product is subjected to ring closurewith urea, followed by a methacrylation reaction.

When it is desired to extend the bond lengths further at the organiclinkages, various processes are usable. There are, for example, aprocess in which an active hydrogen compound containing an unsaturatedgroup, such as hydroxyethyl (meth)acrylate, an alkylene carbonate, analkylene oxide, an alkylene sulfide, a hydroxyalkyl halide, ahydroxyalkyl sulfonate, an epihalohydrin or the like is reacted with thehydroxy derivative or mercapto derivative available through Route (1),(2), (4) or (5) and also a process in which a halogen is once reactedwith the mercapto derivative to convert it into a thiohalide and anunsaturated compound is then reacted.

To synthesize N,N′-bis(5-acryloylthio-3-thiapentyl)-ethyleneurea, forexample, there is the following process.N,N′-bis(bromoethyl)-ethyleneurea obtained by brominatingN,N′-bis(hydroxyethyl)-ethyleneurea is added dropwise to and reactedwith a salt-forming mixture, which has been obtained by adding causticsoda to 2-mercaptoethanol, to synthesizeN,N′-bis(5-hydroxy-3-thiapentyl)-ethyleneurea.

Thiourea is next reacted to formN,N′-bis(5-mercapto-3-thiapentyl)-ethyleneurea, followed by the reactionof chloropropionic acid chloride to obtain a chloropropionic acidthioester derivative. Finally, a base such as a tertiary amine is addedto conduct a dehydrochlorinating reaction.

When it is desired to introduce halogen atoms such as fluorine atomsinto the novel polymerizable compound according to the presentinvention, there are, as relatively easy processes, a process which usesan already halogenated raw material and a process which uses ahalogenating agent such as fluorine gas, hydrogen fluoride, hydrogenchloride, potassium fluoride, potassium iodide, diethylaminosulfurtrifluoride, 2,2-difluoro-1,3-dimethylimidazolidine, thionyl chloride,phosphorus tribromide or iodine chloride.

In the above processes, it is possible to use, with a view to improvingthe reaction velocities of the respective reactions, an acidcatalyst—such as sulfuric acid, hydrochloric acid, phosphoric acid,acetic acid, boron trifluoride, aluminum chloride, dibutyltin dioxide,dibutyltin dilaurate or tetrabutyl tin—or a basic catalyst—such astriethylamine, pyridine, triethanolamine, triphenylphosphine,tributylphosphine, sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, sodium hydrogencarbonate, potassiumhydrogencarbonate, calcium carbonate, calcium hydroxide, magnesiumhydroxide, sodium formate, sodium methylate, t-butoxy potassium, sodiumhydride or sodium—as much as needed to an extent not causing a problem.

A reaction solvent differs depending on the individual reaction.Described basically, however, any solvent can be used insofar as it doesnot react with the reaction substrate, the reaction agent, the product,the catalyst or the like. Examples of solvents, which are rathercommonly employed, can include acetonitrile, dichloromethane,dichloroethane, chloroform, THF, dioxane, glyme, diglyme,dimethylformamide, N,N′-dimethyl-ethyleneurea, benzene, toluene, xylene,chlorobenzene, dichlorobenzene, hexane, cyclohexane, methanol, andwater.

The polymerizable composition according to the present invention, whichhas been described in [8], contains at least one of the novelpolymerizable compounds described in [5], [6] and [7].

Especially to improve wettability, an organic (co)polymer available froma composition added with a copolymerizable component tends to be morepreferred than an organic polymer available only from the novelpolymerizable compound described in [5], [6] or [7]. Illustrative of thecopolymerizable component are compounds which contain polymerizablefunctional groups such as (meth)acryl group, allyl carbonate group,allyl group, isopropenyl group, vinyl group, (thio)epoxy group,iso(thio)cyanate group, mercapto group, hydroxy group and amino group.Use of a compound containing a polymerizable unsaturated group such as(meth)acryl group, allyl carbonate group, allyl group, isopropenyl groupor vinyl group may bring about preferred results in some instances.

More preferred copolymerizable components are polymerizable compoundseach of which has in its molecule a polar structure the dipolar momentof which is large. Still more preferred are organic polymers each ofwhich has an aprotic polar structure the dipolar moment of which is 3debyes or greater. Examples of effective elements can includeheteroatoms such as oxygen atom, nitrogen atom, phosphorus atom andsulfur atom, while examples of effective structure can includealkylene(thio)urea structure, oxazolidone structure, pyrrolidonestructure, lactone structure, sulfone structure, sulfolane structure,amide structure, alkyl(thio)urea structure, sulfone structure, sulfoxidestructure, piperazin-2,3-dione structure, acetyleneurea structure,caprolactam structure, alkylene carbonate structure, and phosphoric acidester structure.

Among these, particularly effective polymerizable compounds are, forexample, polymerizable compounds having alkylene(thio)urea structure,oxazolidone structure, pyrrolidone structure, sulfolane structure, amidestructure, or sulfone structure.

Describing the copolymerizable components more specifically by compoundnames, examples can include styrene, isopropenylbenzene, divinylbenzene,diisopropenylbenzene ethylene glycol diallyl carbonate, diethyleneglycol diallyl carbonate, glycidyl methacrylate, isocyanatomethacrylate,3-isopropenyl-α,α-dimethylbenzyl isocyanate, vinyl acetate, vinylalcohol, allyl alcohol, (meth)acrylic acid, methyl (meth)acrylate, ethyl(meth)acrylate, hydroxyethyl (meth)acrylate, ethylene glycoldi(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycoldi(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycoldi(meth)acrylate, neopentyl glycol di(meth)acrylate,bis{(meth)acryloyloxy}-benzene, bis{(meth)acryloyloxymethyl}-benzene,2,2-bis{(meth)acryloyloxy-ethyloxy-ethyloxy-phenyl}-propane,2,2-bis{(meth)acryloyloxy-ethyloxy-phenyl}-propane,bis{(meth)acryloyloxymethyl}-cyclohexane,bis{(meth)acryloyloxymethyl}-tricyclo[5.2.1.0.²⁶] decane,trimethylolpropane tris{(meth)acrylate},N,N′,N″-tris(allyl)-isocyanurate,N,N′,N″-tris{(meth)acryloyloxy-ethyl}-isocyanurate,

N-methyl-N′-vinyl-ethyleneurea, N-methoxyethyl-N′-vinyl-ethyleneurea,N,N′-divinyl-ethyleneurea,

N-methyl-N′-allyl-ethyleneurea, N-methoxyethyl-N′-allyl-ethyleneurea,N,N′-diallyl-ethyleneurea,

N-methyl-N′-allyloxycarbonyl-ethyleneurea,N-methoxyethyl-N′-allyloxycarbonyl-ethyleneurea, N,N′-bis(allyloxycarbonyl)-ethyleneurea,

N-methyl-N′-(meth)acryloyl-ethyleneurea,N-methoxyethyl-N′-(meth)acryloyl-ethyleneurea,N,N′-di(meth)acryloyl-ethyleneurea,

N-methyl-N′-allyloxycarbonyloxyethyl-ethyleneurea,N-methoxyethyl-N′-allyloxycarbonyloxyethyl-ethyleneurea,N,N′-bis(allyloxycarbonyloxyethyl)-ethyleneurea,

N-methyl-N′-(meth)acryloyloxyethyl-ethyleneurea,N-methoxyethyl-N′-(meth)acryloyloxyethyl-ethyleneurea,N,N′-bis{(meth)acryloyloxyethyl}-ethyleneurea,

1-methyl-3-vinyl-tetrahydro-2-pyrrolidine,1-methoxyethyl-3-vinyl-tetrahydro-2-pyrrolidine,1,3-divinyl-tetrahydro-2-pyrrolidine,

1-methyl-3-allyl-tetrahydro-2-pyrrolidine,1-methoxyethyl-3-allyl-tetrahydro-2-pyrrolidine,1,3-diallyl-tetrahydro-2-pyrrolidine,

1-methyl-3-allyloxycarbonyl-tetrahydro-2-pyrrolidine,1-methoxyethyl-3-allyloxycarbonyl-tetrahydro-2-pyrrolidine,1,3-bis(allyloxycarbonyl)-tetrahydro-2-pyrrolidine,

1-methyl-3-(meth)acryloyl-tetrahydro-2-pyrrolidine,1-methoxyethyl-3-(meth)acryloyl-tetrahydro-2-pyrrolidine,1,3-di(meth)acryloyl-tetrahydro-2-pyrrolidine,

1-methyl-3-allyloxycarbonyloxyethyl-tetrahydro-2-pyrrolidine,1-methoxyethyl-3-allyloxycarbonyloxyethyl-tetrahydro-2-pyrrolidine,1,3-bis(allyloxy-carbonyloxyethyl)-tetrahydro-2-pyrrolidine,

1-methyl-3-(meth)acryloyloxyethyl-tetrahydro-2-pyrrolidine,1-methoxyethyl-3-(meth)acryloyloxyethyl-tetrahydro-2-pyrrolidine,1,3-bis{(meth)acryloyloxy-ethyl}-tetrahydro-2-pyrrolidine,

N-vinyl-oxazolidone, N-allyl-oxazolidone,N-allyloxycarbonyl-oxazolidone, N-(meth)acryloyl-oxazolidone,N-allyloxycarbonyloxyethyl-oxazolidone,N-(meth)acryloyloxyethyl-oxazolidone, N-vinyl-pyrrolidone,N-allyl-pyrrolidone,

N-allyloxycarbonyl-pyrrolidine, N-(meth)acryloyl-pyrrolidone,N-allyloxycarbonyloxyethyl-pyrrolidone,N-(meth)acryloyloxyethyl-pyrrolidone,

N-vinyl-N-methyl-acetamide, N-allyl-N-methyl-acetamide,N-allyloxycarbonyl-N-methyl-acetamide,N-(meth)acryloyl-N-methyl-acetamide,N-allyloxycarbonyl-oxyethyl-N-methyl-acetamide,N-(meth)acryloyloxyethyl-N-methyl-acetamide,

N,N-dimethyl-(meth)acrylamide, N,N-dimethyl-(meth)vinylamide,N,N-dimethyl-(meth)allylamide, N,N-dimethyl-(meth)allyloxycarbonylamide,

N,N′-dimethyl-N,N′-divinylurea, N,N′-dimethyl-N,N′-diallylurea,divinylsulfone, and diallylsulfone. It should however be borne in mindthat the present invention is not limited only to these exemplifiedcompounds.

Depending on the desired physical properties, characteristics, purpose,application and the like, it is also possible to optionally contain,polymerizable compounds other than those described above, chainextenders, crosslinking density improvers, curing agents, catalysts,co-catalysts, photopolymerization initiators, photosensitizers,retarders, polymerization inhibitors, ultraviolet absorbers,stabilizers, colorants, paints, pigments, dyes, inks, photosensitizers,luminescent agents, fragrances, bactericides, binders, fillers,polymers, fillers, glass, metals, metal oxides, organometals, salts,extenders, mold releasing agents, surfactants, foaming-agents, carbondioxide gas, air, inert gas, water, solvents, impurities, additives, andother organic or inorganic compounds, as needed to an extent not causinga problem.

The organic polymer according to the present invention can be obtainedby polymerizing the polymerizable compound or the polymerizablecomposition. As polymerization processes, solution polymerization andbulk polymerization are representative. Bulk polymerization, which doesnot require any cumbersome operation such as solvent recovery, can bepreferably used, although the polymerizable compound or compositionaccording to the present invention can also be polymerized by solutionpolymerization.

In bulk polymerization, thermal polymerization and radiation-inducedpolymerization are representative. In the present invention, one ofthese polymerization processes can also be chosen as desired dependingon the purpose.

Compared with thermal polymerization, radiation-induced polymerizationis limited in the kind, number and the like of compounds. Nonetheless,polymerization itself proceeds extremely fast and in some instances, maybe completed in as short as several seconds. Further, simple andwidely-applicable polymerization making use of sunlight or the like isalso feasible, and can be considered to be a production process havingan extremely high value from the industrial standpoint.

Use examples of these polymerization processes will now be described.For example, thermal polymerization tends to be chosen in the case oflarge, molded or otherwise formed products. There is however a tendencyto choose radiation-induced polymerization when a product to be moldedor otherwise formed is small and is desired to be produced in a shorttime. In the case of ultra-large area painting represented by thepainting of an exterior wall, radiation-induced polymerization makinguse of sunlight tends to be chosen, but for painting a relatively smallarea, there is a tendency to choose one of thermal polymerization andradiation-induced polymerization as desired.

Thermal polymerization in the present invention is generally conductedby heating and polymerizing a compound according to the presentinvention, which contains a polymerizable functional group, or apolymerizable composition containing the same. Heating temperature isgenerally in a range of from room temperature to the Tg of the targetpolymer or higher or in a range not higher than 300° C. As analternative, the temperature may be raised gradually from roomtemperature or so in accordance with the progress of the polymerization.

When thermal polymerization is conducted, a thermal polymerizationcatalyst such as a radical catalyst, anionic catalyst or cationiccatalyst is generally added as needed.

Illustrative of the radical catalyst are azoisobutyronitrile, benzoylperoxide, di-3-methoxybutyl peroxydicarbonate, diisopropylperoxydicarbonate, α-cumyl peroxyneodecanoate, t-butylperoxy-2-ethylhexanoate, dicumyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butylcumyl peroxide.

Illustrative of the anionic catalyst are tetrabutylammonium chloride,tetrabutylammonium hydroxide, triethylamine, tributylamine, pyridine,N-methylpyrrolidone, piperazine, triphenylphosphine, tributylphosphine,triethanolamine, methyldiethanolamine, triisopropanolamine,4,4″-dimethylamino-benzopheone, 2-dimethylaminoethylbenzoic acid, ethyldimethylaminobenzoate, isoamyl dimethylaminobenzoate, (n-butoxy)ethyldimethylaminobenzoate, isoamyl 2-dimethylaminoethylbenzoate,2-ethylhexyl 2-dimethyl-aminoethylbenzonate, sodium acetate, potassiumphosphate, and sodium methoxide.

Illustrative of the cationic polymerization catalyst are sulfuric acid,hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acidphosphoric acid, acetic acid, propionic acid, dibutyltin dioxide,dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate,tetrabutyl tin, boron trifluoride, boron trifluoride-diethyl ethercomplex, tetraethoxytitanium, titanium oxide, aluminum oxide, andaluminum fluoride.

The amount of such a thermal polymerization catalyst to be added cannotbe specified because it varies considerably depending on the kind of thepolymerizable compound or the kind of the composition containing thesame. Nonetheless, it can be added preferably in a range of from about0.0001 to 10 wt. %, more preferably in a range of from 0.001 to 5 wt. %,based on the polymerizable compound or composition according to thepresent invention.

Examples of radiation usable in the present invention can includevisible light of 400 to 800 nm, ultraviolet rays of 400 nm or shorter,and electron beams. In general, use of relatively economical ultravioletrays or visible light is preferred than electron beams which require acostly apparatus.

Electron beams are, however, extremely effective when ultraviolet raysor visible light does not transmit.

When polymerization is conducted with ultraviolet rays, for example, alight source such as a low-pressure mercury vapor lamp, high-pressuremercury vapor lamp, ultra high-pressure mercury vapor lamp, metal halidelamp, pulsed xenon lamp, ultraviolet laser or electrodeless dischargelamp is preferably employed.

Radiation-induced polymerization in the present invention is performedby exposing the polymerizable compound or composition according to thepresent invention to radiation. Thermal polymerization may also be usedin combination as needed.

In addition to the photopolymerization initiator, the above-describedradical catalyst, anionic catalysts or cationic catalyst useful inthermal polymerization may also be used in combination.

Electron beam polymerization may not require any catalyst in someinstances. However, a catalyst may be added to an extent not causing aproblem.

Illustrative of the photopolymerization initiator are light-activatedradical generators, light-activated anion generators, light-activatedcation generators, and the like. Among these, light-activated radicalgenerators and light-activated cation generators can be used preferably.

Examples of the light-activated radical generators can include 4-phenoxydichloroacetophenone, 4-t-butyldichloro-acetophenone,diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one,4-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone,2-methyl-1-{4-(methylthio)phenyl}-2-morphorylpropane-1, benzoin, benzoinmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoinisobutyl ether, benzyldimethylketal, benzophenone, benzoylbenzoic acid,methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone,allylbenzophenone,4-benzoyl-4′-methyldiphenylsulfide-3,3′-dimethyl-4-methoxybenzophenone,thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone,isopropylthioxanthone, 2,4-dichiorothioxanthone,2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,2,4-diisopropylthioxanthone,1-phenyl-1,2-propandione-2-(O-ethoxycarbonyl)oxime,2,4,6-trimethylbenzoyl-diphenylphosphine oxide, methylphenyl glyoxylate,dibenzyl, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone,2-ethylanthraquinone, 4′,4″-diethylisophthaloquinone,3,3′,4,4′-tetra(t-butyl-peroxycarbonyl)benzophenone.

The amount to be added cannot be specified, because it considerablyvaries depending on the kind of the polymerizable compound orpolymerizable composition. Nonetheless, it can be added preferably in arange of from about 0.0001 to 10 wt. %, more preferably in a range offrom 0.001 to 5 wt. %, based on the polymerizable compound orcomposition according to the present invention.

Examples of the light-activated cation generators can include aromaticdiazonium complexes, aromatic sulfonium complexes, aromatic iodoniumcomplexes, Brønsted acid-onium complexes, and Brønsted acid-ironaromatic compound complexes. However, aromatic sulfonium complexes,aromatic iodonium complexes and Brønsted acid-iron aromatic compoundcomplexes can be used preferably in many instances.

Examples of the aromatic sulfonium complexes can includetriphenylsulfonium tetrafluoroborate, triphenylsulfoniumhexafluorophosphonate, triphenylsulfonium hexafluoroarsenate,triphenylsulfonium hexafluoroantimonate, diphenyliodoniumtetrafluoroborate, diphenyliodonium hexafluorophosphonate,diphenyliodonium hexafluoroarsenate, and diphenyliodoniumhexafluoroantimonate. There are also “Cyracure UVI-6974” (trade name,product of UCC), “Cyracure UVI-6990” (trade name, product of UCC),“Optomer SP150” (trade name, product of Asahi Denka Kogyo K. K.) and“Optomer SP170” (trade name, product of Asahi Denka Kogyo K. K.), all ofwhich are commercially available as improved products of such aromaticsulfonium complexes and also generate free radicals.

As a Brønsted acid-iron aromatic compound complex, there is “CG24-061”(trade name, product of Ciba Geigy).

The amount of such a light-activated cation generator to be added cannotbe specified because it varies considerably depending on the kind of thepolymerizable compound or polymerizable composition. Nonetheless, it canbe added preferably in a range of from about 0.0001 to 10 wt. %, morepreferably in a range of from 0.001 to 5 wt. %, based on thepolymerizable compound or composition according to the presentinvention.

If a desired polymerization rate cannot be achieved, for example, invisible light induced polymerization making combined use of aphotopolymerization initiator and a thermal polymerization catalyst, onthe other hand, addition of a photosensitizer such as camphorquinone maybe effective in some instances.

The organic polymers and the molded or otherwise formed productscomprising the same, to both of which the present invention relates, arehigh in hydrophilicity and tend to be wet with water. Even if ordinarywater-insoluble components which remain as pollutants, air-bornehydrophobic substances, or hydrophobic pollutants such as cokecomponents from automobile exhaust, industrial exhaust or the like,sebum and proteins deposit, the pollutants are caused to separate bywater such as rain, shower, tear or the like and thus, are eliminated(self-cleaning). In addition, formation of water droplets and mist onwindow panes, mirrors, agricultural vinyl sheets, spectacle lenses,camera lenses and the like under high-humidity conditions and formationof dews on interior walls and upholstery can also be suppressed.Obviously, they can also be applied as materials for suppressing areduction in the efficiency of heat exchange due to the formation ofwater droplets and deposition of fouling substances on cooling fins.

The organic polymers according to the present invention, which are highin water wettability and are hydrophilic, are highly compatible withsteam, water and the like and can easily absorb and retain them.Accordingly, they can also be applied as water retaining materialsuseful for greening deserts or promoting the growth of general plants,and like purposes and also as waste water (liquid) absorbent materialsand the like.

In the field of optical materials, such as spectacle lenses, contactlenses, camera lenses and pickup lenses, for which transparency isimportant, the organic polymers according to the present invention canalso improve their dyeability with disperse dyes and contact lens wearcomfort in addition to their antifouling properties.

As described above, the organic polymers according to the presentinvention and the molded or otherwise formed products, which contain theorganic polymers and also pertain to the present invention, can besuitably used in the fields of antifouling (including coating) materials(self-cleaning materials), dew preventing materials, water (liquid)absorbent materials, optical materials and the like.

In addition, they can be used in various fields, for example, such asship bottom painting materials; body fluid absorbents such as gauze,first-aid straps and diapers; plasters such as poultices;medicament-containing adhesive materials such as fragrance preparations;gel materials for cold insulators; road anti-freezing materials;concrete additives; (photocuring) adhesive materials; tape materials;photocuring dental materials; display partition materials; hairdressingadditives; additives to surfactants such as hair shampoos, hair rinses,hair conditioners, and body washes or shampoos; surfactants;(photocuring) inks; (photocuring) paints and coating materials;letterpress materials; additives to inkjet inks; additives to inkjetsheets and copy papers; (color) toner materials; binders for magneticdisks and magnetic tapes; photoresist materials; film resist materials;superconductor matrix materials; blood storage containers; materials formolded or otherwise formed plastic products; and curing polymerizablecompounds.

The present invention will hereinafter be described in further detail onthe basis of Examples. It should however be borne in mind that thepresent invention is not limited only to these Examples.

Further, a series of operations and the like upon synthesis of polymerswere conducted at room temperature unless otherwise specificallyindicated.

For the measurement of water contact angles, “CA-X200 Model” (tradename; manufactured by KYOWA INTERFACE SCIENCE CO., LTD.) was used.

EXAMPLE 1

Synthesis of chloroethyloxazolidone (hereinafter abbreviated as “CEOZ”)and N-methoxyethyl-N′-hydroxy-ethyl-ethyleneurea (abbreviated as “MHEU”)

97% Sodium hydroxide (173.2 g, 4.20 mol), sodium hydrogencarbonate(378.0 g, 4.50 mol) and water (1,500 mL) were mixed into a homogeneoussolution.

To the solution, bis(2-chloroethyl)amine hydrochloride (750.0 g, 4.20mol) was added in portions at internal temperatures of from 30 to 35° C.over 0.5 hour, followed by aging at 40° C. for 4 hours. Chloroform (0.5L) was added with stirring to the reaction mixture, allowed to stand, aseparated lower organic layer was collected. An upper water layer wasextracted with three 0.5 L portions of chloroform (total: 1.5 L) tocollect organic components. Those chloroform layers were combined anddistilled off the solvent to afford CEOZ of 93.2% purity (569.8 g, 3.55mol, pure yield: 84.5%).

The followings are identification data of the thus-obtained CEOZ:

¹H-NMR→See FIG. 1

¹³C-NMR→See FIG. 2

To 2-methoxyethylamine (1,350 g, 18.0 mol), the CEOZ of 93.2% purity(3.54 mol) was then added dropwise under reflux (93 to 102° C.) over 1hour, followed by aging under reflux (102 to 105° C.) for 15 hours.

To the reaction mixture, a 38.7 wt. % aqueous solution of sodiumhydroxide (366.0 g, 3.54 mol) was added at internal temperatures of from20 to 35° C. to neutralize the reaction mixture. Water was eliminated onan evaporator, and the precipitated salt was collected by filtration andwashed with ethyl acetate. The resulting filtrate and washings werecombined and concentrated again on the evaporator. Finally, the residuewas purified by chromatography on a silica gel column to afford MHEU of99% purity (471.5 g, 2.48 mol, pure yield: 70%).

The followings are identification data of the thus-obtained CEOZ:

¹H-NMR→See FIG. 3

¹³C-NMR→See FIG. 4

EXAMPLE 2

Synthesis of N-methoxyethyl-N′-mercaptoethyl-ethyleneurea (abbreviatedas “THEU”)

To N-methoxyethyl-N′-hydroxyethyl-ethylene urea (MHEU) of 99% purity(110.0 g, 0.579 mol), phosphorus tribromide (58.0 g, 0.214 mol) wasadded dropwise at internal temperatures of from 10 to 40° C., followedby aging at 50° C. for 2 hours. Chloroform (200 mL) was added to thereaction mixture, and water (50 mL) was added dropwise at an internaltemperature of 60° C. The mixture was allowed to cool down to roomtemperature and also to separate into layers. The resulting organiclayer was concentrated under reduced pressure to afford crudeN-methoxyethyl-N′-bromoethyl-ethyleneurea (130.5 g, 0.520 mol, crudeyield: 90%).

To the crude N-methoxyethyl-N′-bromoethyl-ethyleneurea, thiourea (69.6g, 0.914 mol) and water (300 mL) were added, followed by a reactionunder reflux (100 to 102° C.) for 3 hours. Subsequent to cooling to 40°C., 28% aqueous ammonia (148.0 g, 2.44 mol) was added dropwise at from40 to 46° C. and the resulting mixture was allowed to age at 55° C. for3 hours.

After the reaction mixture was allowed to cool down to room temperature,the resultant reaction mixture was extracted three times withchloroform. The thus-obtained organic layer was washed with hydrochloricacid, an aqueous solution of sodium hydrogencarbonate, and saline, andwas then concentrated under reduced pressure. Finally, the resultingresidue was purified by chromatography on a silica gel column to affordTHEU of 92% purity (68.0 g, 0.306 mol, pure yield: 52.9%/MHEU).

The followings are identification data of the thus-obtained THEU:

¹H-NMR→See FIG. 5

IR→See FIG. 6

EXAMPLE 3

Synthesis of N,N′-bis(hydroxyethyl)-ethyleneurea (abbreviated as “HEEU”)and N,N′-bis(mercaptoethyl)-ethyleneurea (abbreviated as “DMEU”)

To 2-aminoethanol (1,180.0 g, 19.3 mol), CEOZ of 93.2% purity (568.0 g,3.54 mol) was added dropwise at from 105 to 110° C. over 1 hour,followed by aging at 110° C. for 3 hours. Subsequent to cooling, anaqueous solution of 97% sodium hydroxide (146.0 g, 3.54 mol) and water(220 mL) was added, and filtration was then conducted. Anhydrousmagnesium sulfate was added to the filtrate, and filtration wasconducted again. The filtrate was caused to flow through a silica gelpacked column, and the column was washed with methanol. The columneffluent and the washing (methanol solution) were combined, anddistilled under reduced pressure to distill off the solvent,2-aminoethanol used in excess, etc. The resulting residue was purifiedby chromatography on a silica gel column to afford HEEU of 99% purity(469.4 g, 2.67 mol, pure yield: 75.4%).

The followings are identification data of the thus-obtained HEEU:

¹H-NMR→See FIG. 7

¹³C-NMR→See FIG. 8

To a liquid mixture of HEEU of 99% purity (150.6 g, 0.856 mol) andchloroform (60 mL), phosphorus tribromide (168.0 g, 0.605 mol) was addeddropwise at internal temperatures of from 45 to 60° C., followed byaging at from 50 to 80° C. for 3 hours. The thus-obtained reactionmixture was allowed to cool down to room temperature, and water (30 ml)was added dropwise to hydrolyze excess phosphorus tribromide. Chloroformand water were then added to conduct water washing. The resultingorganic layer was concentrated under reduced pressure to afford crudeN,N′-bis(bromoethyl)-ethyleneurea (252.7 g, 0.842 mol, crude yield:98%).

To the crude N,N′-bis(bromoethyl)-ethyleneurea, thiourea (200.0 g, 2.63mol), 98% sulfuric acid (0.5 mL) and water (250 mL) were added, followedby a reaction under reflux (105° C.) for 3 hours. After being cooled to40° C., 25% aqueous ammonia (230.0 g, 3.38 mol) was added dropwise atfrom 40 to 50° C., and a reaction was conducted at 65° C. for 3 hours.

After the reaction mixture was allowed to cool down to room temperature,sodium chloride was added and the resultant solution was extracted threetimes with chloroform. The thus-obtained organic layer was washed withhydrochloric acid, an aqueous solution of sodium hydrogencarbonate, andsaline, and was then concentrated under reduced pressure. The resultingresidue was purified by chromatography on a silica gel column to affordDMEU of 95% purity (134.0 g, 0.617 mol, pure yield: 72.1%/MHEU).

The followings are identification data of the thus-obtained DMEU:

¹H-NMR→See FIG. 9

¹³C-NMR→See FIG. 10

EXAMPLE 4

Synthesis of N-methoxyethyl-N′-methacryloyloxy-ethyl-ethyleneurea(hereinafter abbreviated as “MEMEU”)

To a liquid mixture of MHEU of 99% purity (180.0 g, 0.947 mol),triethylamine (95.7 g, 0.947 mol) and EDC (dichloroethane, 240 g),methacrylic acid chloride (99.0 g, 0.947 mol) was added dropwise atinternal temperatures of from 5 to 20° C. over 1 hour, followed by agingat from 10 to 22° C. for 1 hour. The reaction mixture was washed withEDC, water and 35% hydrochloric acid, concentrated under reducedpressure on an evaporator. The residue was purified by chromatography ona silica gel column.

As a result, N-methoxyethyl-N′-methacryloyloxy-ethyl-ethyleneurea(hereinafter abbreviated as “MEMEU”) of 97% purity was obtained in anamount of 197.1 g (0.746 mol, pure yield: 78.8%).

The followings are identification data of the thus-obtained MEMEU:

¹H-NMR→See FIG. 11

¹³C-NMR→See FIG. 12

EXAMPLE 5

Synthesis of N-methoxyethyl-N′-acryloylthioethyl-ethyleneurea(abbreviated as “ATEMU”)

To MHEU of 99% purity (110.0 g, 0.579 mol), phosphorus tribromide (58.0g, 0.214 mol) was added dropwise at internal temperatures of from 10 to40° C., followed by aging at 50° C. for 2 hours. Chloroform (200 mL) wasadded to the thus-obtained reaction mixture, and water (50 mL) was addeddropwise at an internal temperature of 60° C. The thus-prepared mixturewas allowed to cool down to room temperature and also to separate intolayers. The resulting organic layer was concentrated under reducedpressure to afford crude N-methoxyethyl-N′-bromoethyl-ethyleneurea(130.5 g, crude yield: 88%).

To the N-methoxyethyl-N′-bromoethyl-ethyleneurea, thiourea (69.6, 0.915mol) and water (300 mL) were added, followed by a reaction under reflux(100 to 102° C.) for 3 hours. Subsequent to cooling to 40° C., 28%aqueous ammonia (148.0 g, 2.44 mol) was added dropwise at 40 to 46° C.and the resulting mixture was allowed to age at 55° C. for 3 hours.

After the reaction mixture was allowed to cool down to room temperature,the resultant reaction mixture was extracted three times withchloroform. The thus-obtained organic layer was washed with hydrochloricacid, an aqueous solution of sodium hydrogencarbonate, and saline, andwas then concentrated under reduced pressure to afford crudeN-methoxyethyl-N′-mercaptoethyl-ethyleneurea (68.0 g, crude yield:57.5%/MHEU).

To the crude N-methoxyethyl-N′-mercaptoethyl-ethyleneurea (68.0 g),chloropropionic acid chloride (43.2 g, 0.340 mol) was added dropwise atinternal temperatures of from 30 to 40° C., followed by aging at 40° C.for 3 hours.

Chloroform (140 mL) was then added, triethylamine (61.9 g, 0.602 mol)was added dropwise at internal temperatures of from 5 to 15° C. over 1hour, followed by aging at internal temperatures of from 20 to 30° C.for 1 hour.

To the reaction mixture, chloroform (850 mL) and water (350 mL) wereadded to extract and wash. The separated organic layer was washed withhydrochloric acid and water, dried over anhydrous magnesium sulfate, andthen filtered. The resulting filtrate was concentrated under reducedpressure, and the residue was purified by chromatography on a silica gelcolumn to afford N-methoxyethyl-N′-acryloylthioethyl-ethyleneurea(ATEMU) of 95% purity (65.5 g, 0.241 mol, pure yield: 41.6%/MHEU).

The followings are identification data of the thus-obtained ATEMU:

¹H-NMR→See FIG. 13

IR→See FIG. 14

EXAMPLE 6

Synthesis of N-methoxyethyl-N′-allylthiocarbonato-ethyl-ethyleneurea(abbreviated as “ATMEU”)

To a liquid mixture of N-methoxyethyl-N′-mercaptoethyl-ethyleneurea(THEU) (80.0 g, 0.392 mol), triethylamine (71.4 g, 0.705 mol) andtoluene (200 mL), allyl chloroformate (85.0 g, 0.705 mol) was addeddropwise at internal temperatures of from 3 to 15° C. over 2 hours,followed by aging at from 10 to 20° C. for 2 hours. Chloroform (400 mL)and water (400 mL) were then added to extract the reaction mixture andto separate the same into layers. The organic layer was washed twicewith water (400 mL), dried over anhydrous magnesium sulfate, and thenfiltered. The filtrate was concentrated on an evaporator. Finally, theresidue was purified by chromatography on a silica gel column to affordN-methoxyethyl-N′-allylthiocarbonatoethyl-ethyleneurea (hereinafterabbreviated as “ATMEU”) of 94% purity (105.6 g, 0.344 mol, pure yield:87.8%/THEU).

The followings are identification data of the thus-obtained ATMEU:

¹H-NMR→See FIG. 15

¹³C-NMR→See FIG. 16

EXAMPLE 7

Synthesis of N-methoxyethyl-N′-allylcarbonatoethyl-ethyleneurea(abbreviated as “ACMEU”)

To a liquid mixture of N-methoxyethyl-N′-hydroxyethyl-ethyleneurea(MHEU) (73.8 g, 0.392 mol), triethylamine (71.4 g, 0.705 mol) andtoluene (200 mL), allyl chloroformate (85.0 g, 0.705 mol) was addeddropwise at internal temperatures of from 3 to 15° C. over 2 hours,followed by aging at from 10 to 20° C. for 2 hours. After completion ofthe reaction, toluene (500 mL) was added, and the resulting mixture wasfiltered. The filtrate was concentrated on an evaporator. Finally, theresidue was purified by chromatography on a silica gel column to affordN-methoxyethyl-N′-allylcarbonatoethyl-ethyleneurea (ACMEU) of 93% purity(100.4 g, 0.343 mol, pure yield: 87.5%/MHEU).

The followings are identification data of the thus-obtained ACMEU:

¹H-NMR→See FIG. 17

¹³C-NMR→See FIG. 18

EXAMPLE 8

Synthesis of N-methoxyethyl-N′-(glycidyloxyethyl)-ethyleneurea(abbreviated as “EPMEU”)

To a liquid mixture of MHEU of 99% purity (100.0 g, 0.526 mol),epichlorohydrin (147.1 g, 1.59 mol) and dimethyl sulfoxide (30 g), 40%caustic soda (53.0 g, 0.530 mol) was added dropwise at internaltemperatures of from 25 to 40° C. over 1 hour, followed by aging at from40 to 60° C. for 8 hours. The reaction solution was filtered, and thefiltrate was concentrated under reduced pressure on an evaporator.Acetonitrile was added to the residue, the resulting mixture wasfiltered, and the filtrate was again concentrated under reduced pressureon the evaporator. The residue was purified by chromatography on asilica gel. As a result,N-methoxyethyl-N′-(glycidyloxyethyl)-ethyleneurea (EPMEU) of 95% puritywas obtained in an amount of 69.0 g (0.268 mol, pure yield: 51%/MHEU).

The followings are identification data of the thus-obtained EPMEU:

¹H-NMR→See FIG. 19

IR→See FIG. 20

EXAMPLE 9

Synthesis of N,N′-bis(methacryloyloxyethyl)-ethyleneurea (abbreviated as“MEEU”)

To a liquid mixture of HEEU of 99% purity (200.0 g, 1.14 mol),triethylamine (232.7 g, 2.30 mol) and acetonitrile (1,000 mL),methacrylic acid chloride (240.4 g, 2.30 mol) was added dropwise at from5 to 10° C. over 1 hour, followed by aging at from 10 to 25° C. for 3hours. After the reaction mixture was filtered, the filtrate wasneutralized with acetic acid, p-methoxyphenol (2.0 g) was added, and at30° C. or lower, distilled off the solvent under reduced pressure. Theconcentration residue was diluted with toluene, filtered again. Thethus-obtained filtrate was distilled off the solvent at 30° C. or lowerunder reduced pressure. Finally, the resulting residue was purified bychromatography on a silica gel column. In the course of concentration,methoxyphenol (2.0 g) was added once again to affordN,N′-bis(methacryloyloxy-ethyl)-ethyleneurea (MEEU) of 97% purity (211.6g, 0.661 mol, pure yield: 58.0%).

The followings are identification data of the thus-obtained MEEU:

¹H-NMR→See FIG. 21

¹³C-NMR→See FIG. 22

EXAMPLE 10

Synthesis of N,N′-bis (allylcarbonatoethyl)-ethyleneurea (abbreviated as“ACEU”)

To a liquid mixture of HEEU of 99% purity (100.0 g, 0.568 mol),triethylamine (116.4 g, 1.15 mol) and acetonitrile (500 mL), allylchloroformate (150.7 g, 1.25 mol) was added dropwise at from 5 to 10° C.over 1 hour, followed by aging at from 10 to 25° C. for 5 hours. Afterthe reaction mixture was filtered, distilled off the solvent at 30° C.or lower under reduced pressure. The concentration residue was dilutedwith toluene, filtered again. The thus-obtained filtrate was againdistilled off the solvent at 30° C. or lower under reduced pressure. Theresulting residue was purified by chromatography on a silica gel columnto afford N,N′-bis(allylcarbonato-ethyl)-ethyleneurea (ACEU) of 94%purity (160.2 g, 0.440 mol, pure yield: 77.5%).

The followings are identification data of the thus-obtained ACEU:

¹H-NMR→See FIG. 23

¹³C-NMR→See FIG. 24

EXAMPLE 11

Synthesis of N,N′-bis(acryloylthio-ethyl)-ethyleneurea (abbreviated asATEEU)

To a liquid mixture of DMEU of 95% purity (100.0 g, 0.460 mol) andacetonitrile (120 mL), chloropropionic acid chloride (128.5 g, 1.01 mol)was added dropwise at 40 to 55° C., followed by aging at 40° C. for 6hours while slightly bubbling the liquid reaction mixture with nitrogen.After the reaction mixture was allowed to cool down to room temperature,toluene (200 mL) was added, triethylamine (144.0 g, 1.42 mol) was addeddropwise at from 0 to 10° C., followed by aging at from 10 to 15° C. for5 hours. To the reaction mixture, water, saline and chloroform wereadded to extract and wash the same. After the organic layer was washedwith hydrochloric acid and water, methoxyphenol (0.1 g) was added, andthe solvent was then removed at 20° C. or lower on an evaporator. Theremaining residue was purified by chromatography on a silica gel. In thecourse of concentration, methoxyphenol (0.4 g) was added once again toafford N,N′-bis(acryloylthio-ethyl)-ethyleneurea (ATEEU) of 98% purity(80.0 g, 0.249 mol, pure yield: 54.1%).

The followings are identification data of the thus-obtained ATEEU:

¹H-NMR→See FIG. 25

¹³C-NMR→See FIG. 26

EXAMPLE 12

Synthesis of N,N′-bis(allylthiocarbonatoethyl)-ethyleneurea (abbreviatedas “ATCEU”)

To a liquid mixture of DMEU of 95% purity (100.0 g, 0.460 mol),triethylamine (100.0 g, 0.988 mol) and acetonitrile (500 mL), allylchloroformate (119.1 g, 0.988 mol) was added dropwise at from 5 to 10°C. over 1 hour, followed by aging at from 10 to 25° C. for 5 hours.After the reaction mixture was filtered, concentrated at 30° C. or lowerunder reduced pressure. The concentration residue was diluted withtoluene, and filtered again. The thus-obtained filtrate was concentratedat 30° C. or lower under reduced pressure. Finally, the resultingresidue was purified by chromatography on a silica gel column to affordN,N′-bis(allylthiocarbonatoethyl)-ethyleneurea (ATCEU) of 85% purity(141.4 g, 0.321 mol, pure yield: 69.8%).

The followings are identification data of the thus-obtained ATCEU:

¹H-NMR→See FIG. 27

¹³C-NMR→See FIG. 28

EXAMPLE 13

Synthesis of N,N′-bis(glycidylthioethyl)-ethyleneurea (abbreviated as“GTEU”)

To DMEU of 95% purity (100.0 g, 0.460 mol), a 49% aqueous solution ofsodium hydroxide (75.1 g, 0.920 mol) was added dropwise at from 15 to25° C. over 1 hour, followed by aging at 20° C. for 0.5 hours. Further,epichlorohydrin (85.1 g, 0.920 mol) was added dropwise at from 30 to 35°C. over 2 hours, followed by aging at 40° C. for 2 hours. To thereaction mixture, chloroform and water were added to extract and washthe same. The thus-obtained organic layer was washed once again withwater, dried over anhydrous magnesium sulfate, and filtered. Thefiltrate was concentrated on an evaporator.

The residue so obtained was purified by chromatography on a silica gelto afford N,N′-bis(glycidylthio-ethyl)-ethyleneurea (GTEU) of 94% purity(11.4 g, 0.034 mol, pure yield: 7.4%).

The followings are identification data of the thus-obtained GTEU:

¹H-NMR→See FIG. 29

¹³C-NMR→See FIG. 30

EXAMPLE 14

Synthesis of N,N′-bis(hydroxymethyl)-ethyleneurea (abbreviated as“HMEU”) and N,N′-bis(methacryloyloxy-methyl)-ethyleneurea (abbreviatedas “MMEU”)

Ethyleneurea (161.6 g, 1.88 mol), paraformaldehyde (128.5 g, 4.28 mol asformaldehyde), a 28 wt. % solution of sodium methylate in methanol (2.3g) and methanol (550 mL) were charged in a reactor and reacted at 55° C.for 5 hours. The reaction mixture was concentrated under reducedpressure. The residue was recrystallized form acetonitrile to affordHMEU of 92% purity (168.1 g, 1.06 mol, pure yield: 56.4%).

To a liquid mixture of HMEU of 92% purity (100.0 g, 0.630 mol),triethylamine (138.5 g, 1.37 mol) and acetonitrile (400 mL), methacrylicacid chloride (143.0 g, 1.37 mol) was added dropwise at from 10 to 30°C. over 1 hour, followed by aging at 20° C. for 1 hour. After thereaction mixture was filtered, the filtrate was neutralized,p-methoxyphenol (0.2 g) was added, concentrated at 30° C. or lower underreduced pressure.

To the residue, dichloromethane and diluted hydrochloric acid were addedto extract and wash. The thus-obtained organic layer was then washedthree times with water, p-methoxyphenol (0.1 g) was added again, and at30° C. or lower, distilled off the solvent under reduced pressure.Finally, the residue was purified by chromatography on a silica gelcolumn. In the course of concentration, methoxyphenol (0.1 g) was addedonce again to afford N,N′-bis(methacryloyloxymethyl)-ethyleneurea (MMEU)of 94% purity (58.0 g, 0.193 mol, pure yield: 30.6%).

The followings are identification data of the thus-obtained MMEU:

¹H-NMR→See FIG. 31

¹³C-NMR→See FIG. 32

EXAMPLE 15

Synthesis of N,N′-bis(glycidyloxyethyl)-ethyleneurea (abbreviated as“DGEEU”)

To a liquid mixture of HEEU of 99% purity (500.0 g, 2.84 mol),epichlorohydrin (1,471 g, 15.9 mol) and dimethyl sulfoxide (250 g), 40%caustic soda (574 g, 5.74 mol) was added dropwise at internaltemperatures of from 25 to 40° C. over 1 hour, followed by aging at 40°C. for 8 hours. The reaction mixture was filtered, concentrated underreduced pressure on an evaporator. Acetonitrile was added to theresidue, the resulting mixture was filtered, concentrated again underreduced pressure on the evaporator. The residue was purified bychromatography on a silica gel. As a result,N,N′-bis(glycidyloxyethyl)-ethyleneurea (DGEEU) of 95% purity wasobtained in an amount of 146.0 g (0.484 mol, pure yield: 17%/HEEU).

The followings are identification data of the thus-obtained DGEEU:

¹H-NMR→See FIG. 33

IR→See FIG. 34

EXAMPLE 16

Synthesis of N,N′-bis(thioglycidylthioethyl)-ethyleneurea (abbreviatedas “TGEU”)

To a liquid mixture obtained by adding triethylamine (50 g) toN,N′-bis(mercaptoethyl)-ethyleneurea (DMEU) of 93% purity (600 g, 2.69mol), epichlorohydrin (550 g, 5.94 mol) was added dropwise at internaltemperatures of from 35 to 45° C., followed by aging at from 40 to 55°C. for 7 hours. To the reaction mixture, 42.9% caustic soda (560 g, 6.00mol) was further added dropwise at internal temperatures of from 25 to35° C., followed by aging at from 25 to 35° C. for 3 hours. To thethus-obtained reaction mixture, chloroform and water were added to washthe same with water. After washing with diluted hydrochloric acid andwashing with water were successively conducted, the reaction mixture wasconcentrated under reduced pressure on an evaporator to afford crudeN,N′-bis(glycidylthioethyl)-ethyleneurea (1,012 g).

To the thus-obtained crude N,N′-bis(glycidyl-thioethyl)-ethyleneurea,thiourea (900 g, 11.8 mol) and methanol (5,000 mL) were added, followedby a reaction at from 25 to 30° C. for 4 hours. After the reactionmixture was concentrated under reduced pressure on an evaporator,chloroform and water were added to wash the residue, separated anorganic layer. The organic layer was washed with diluted sulfuric acidand water, dried over anhydrous magnesium sulfate, and filtered. Thefiltrate was concentrated again under reduced pressure on an evaporator,and the residue was purified by chromatography on a silica gel column.As a result, N,N′-bis(thioglycidylthioethyl)-ethyleneurea (TGEU) of 99%purity was obtained in an amount of 380 g (1.07 mol, pure yield:40%/DMEU).

The followings are identification data of the thus-obtained TGEU:

¹H-NMR→See FIG. 35

¹³C-NMR→See FIG. 36

EXAMPLE 17

Synthesis of N,N′-bis(2-hydroxy-3-acryloyloxy-propyl)-ethyleneurea(abbreviated as “AHPI”)

Into a reaction flask, ethyleneurea (215.0 g, 2.50 mol), epichlorohydrin(2,313.0 g, 25.0 mol) and trimethylbenzyl chloride (6.5 g) were charged.Under heating and reflux (120° C.), they were reacted for 5 hours, andthe reaction mixture was cooled to 60° C.

97% Sodium hydroxide flakes (250.0 g, 6.0 mol) was then charged inportions while watching the state of the reaction mixture, and aging wasconducted at from 60 to 80° C. for 1.5 hours.

The reaction mixture was allowed to cool down to room temperature, andwas then filtered. The resulting filtrate was concentrated on anevaporator, and the residue was purified by chromatography on a silicagel column. As a result, N,N′-bis(glycidyl)-ethyleneurea (DGEU) of 93%purity was obtained in an amount of 290.0 g (1.36 mol, pure yield:54%/ethyleneurea).

A liquid mixture of the thus-obtained DGEU of 93% purity (105.3 g, 0.494mol) and trimethylbenzyl chloride (5.0 g) was heated to 60° C. Whilemaintaining the internal temperature, chloropropionic acid (108.5 g,1.00 mol) was added dropwise, followed by aging at from 65 to 90° C. for1.5 hours. After the reaction mixture was cooled to 5° C., triethylamine(101.2 g, 1.00 mol) was added dropwise at from 5 to 10° C., followed byaging at from 20 to 30° C. for 1 hour.

The thus-obtained reaction mixture was neutralized with hydrochloricacid, dried over anhydrous magnesium sulfate, and filtered. Finally, thefiltrate was concentrated on an evaporator, and the residue was purifiedby silica gel chromatography. As a result,N,N′-bis(2-hydroxy-3-acryloyloxy-propyl)-ethyleneurea (AHPI) of 92%purity was obtained in an amount of 31.0 g (0.098 mol, pure yield:20%\/DGEU).

The followings are identification data of the thus-obtained AHPI:

¹³C-NMR→See FIG. 37

IR→See FIG. 38

EXAMPLE 18

Synthesis ofN,N′-bis{6-(N-methyl-imidazolidinonyl-N′-)-2-(methacryloyloxy)-4-thiahexyl}-ethyleneurea(abbreviated as “S-3I”)

To a liquid mixture of N-methyl-N′-(2-hydroxyethyl)-ethyleneurea (50.0g, 0.347 mol), which had been synthesized from chloroethyloxazolidoneand methylamine, and chlorobenzene (50 mL), phosphorus tribromide (36.5g, 0.121 mol) was added dropwise at internal temperatures of from 30 to60° C., followed by aging at from 60 to 70° C. for 1 hour. Thiourea(50.0 g, 0.657 mol) and water (50 mL) were then added, heated underreflux (95 to 96° C.) for 3.5 hours. The reaction mixture was cooled to40° C. or so, 25% aqueous ammonia (50.0 g, 0.734 mol) was graduallyadded, hydrolyzed at from 60 to 65° C. for 2.5 hours.

After the reaction mixture was allowed to cool down to room temperature,35% hydrochloric acid (45.0 g, 0.432 mol) and chloroform (300 mL) wereadded to wash the reaction mixture. The organic layer was separated.Chloroform (200 mL) was added once again to the water layer to extractit, and an organic layer was allowed to separate. After the separatedorganic layers were combined and concentrated under reduced pressure,the residue was distilled under reduced pressure to collect a fractionat from 115 to 118° C./200 Pa (1.5 torr). As a result,N-methyl-N′-(2-mercaptoethyl)-ethyleneurea (MEMI) of 99% purity wasobtained in an amount of 43.0 g (0.266 mol, pure yield: 77%).

A liquid mixture of DGEU of 93% purity (21.3 g, 0.10 mol), triethylamine(1.0 g) and acetonitrile (50 mL) was then heated to 75° C., and MEMI of99% purity (32.3 g, 0.20 mol) was added dropwise at from 75 to 80° C.,followed by aging at 80° C. for 4 hours. After the reaction mixture wascooled to 5° C., triethylamine (48.0 g, 0.47 mol) was added, methacrylicacid chloride (50.0 g, 0.48 mol) was added dropwise at internaltemperatures of from 5 to 10° C., followed by aging at from 20 to 30° C.for 1 hour.

Toluene (100 mL) was added to the thus-obtained reaction mixture, andthe resulting mixture was filtered. The filtrate was concentrated on anevaporator, and the resulting residue was purified by silica gelchromatography. As a result,N,N′-bis{6-(N-methyl-imidazolidinonyl-N′-)-2-(methacryloyloxy)-4-thiahexyl}-ethyleneurea(S-3I) of 95% purity was obtained in an amount of 28.6 g (0.042 mol,pure yield: 42%/DGEU).

The followings are identification data of the thus-obtained S-3I:

¹H-NMR→See FIG. 39

¹³C-NMR→See FIG. 40

EXAMPLE 19

Synthesis of N,N′-bis(acryloyloxyethyl)-ethyleneurea (abbreviated as“AEEU”)

To a liquid mixture of HEEU of 99% purity (200.0 g, 1.14 mol),triethylamine (232.7 g, 2.30 mol) and acetonitrile (1,000 mL), acrylicacid chloride (208.2 g, 2.30 mol) was added dropwise at from 5 to 10° C.over 1 hour, followed by aging at from 10 to 25° C. for 3 hours. Afterthe reaction mixture was filtered, the filtrate was neutralized withacetic acid and concentrated at 30° C. or lower under reduced pressure.Toluene was added to the residue, and filtered again. The filtrate wasagain concentrated at 30° C. or lower under reduced pressure. Finally,the thus-obtained residue was purified by chromatography on a silica gelcolumn. In the course of concentration, methoxyphenol (0.2 g) was addedto afford N,N′-bis(acryloyloxyethyl)-ethyleneurea (AEEU) of 96% purity(191.1 g, 0.650 mol, pure yield: 57.0%).

The followings are identification data of the thus-obtained AEEU:

¹H-NMR→See FIG. 41

¹³C-NMR→See FIG. 42

EXAMPLE 20

Synthesis ofN,N′-bis{2-mercaptomethyl-2-(2-mercaptoethylthio)-ethyl}-ethyleneurea(abbreviated as “MESPI”)

A liquid mixture of N,N′-diglycidyl-ethyleneurea (DGEU) (59.4 g, 0.30mol) and triethylamine (3.0 g) was heated to 50° C., and2-mercaptoethanol (47.8 g, 0.61 mol) was added dropwise at from 50 to80° C., followed by aging at 60° C. for 1 hour.

After the reaction mixture was allowed to cool down to room temperature,phosphorus tribromide (109.4 g, 0.40 mol) was added dropwise at from 20to 30° C. over 1 hour, followed by aging at 60° C. for 4 hours. To thethus-obtained reaction mixture, chloroform (400 mL) and water (200 mL)were added for extraction, and the organic layer was concentrated underreduced pressure to afford crudeN,N′-bis{2-bromo-3-(2-bromoethylthio)-propyl}-ethyleneurea (165.0 g,0.272 mol, crude yield: 90.6%/DGEU).

Thiourea (166 g, 2.19 mol) and water (200 mL) were next added to theresulting bromo derivative (155.0 g, 0.26 mol), and the resultingmixture was heated under stirring and reflux for 4 hours (internaltemperature: 100 to 102° C.).

After the reaction mixture was cooled to 40° C., 28 wt. % aqueousammonia (198.0 g, 3.27 mol) was added dropwise at internal temperaturesof from 40 to 45° C. over 30 minutes, followed by aging at 50° C. for 2hours.

The thus-obtained reaction mixture was extracted with chloroform (300mL) three times (900 mL in total). The combined organic layer was washedwith hydrochloric acid, an aqueous solution of sodium carbonate andwater, and was then concentrated under reduced pressure to afford MESPI(109.3 g, 0.26 mol). Finally, the crude MESPI was purified by silica gelchromatography to afford crudeN,N′-bis{2-mercaptomethyl-2-(2-mercaptoethylthio)-ethyly}-ethyleneurea(MESPI) (73.0 g, 0.17 mol, pure yield: 60%/DGEU).

The followings are identification data of the thus-obtained MESPI:

¹H-NMR→See FIG. 43

¹³C-NMR→See FIG. 44

EXAMPLE 21

Synthesis of N,N′-diallyl-ethyleneurea (abbreviated as “DAEU”)

To a liquid mixture of 60 wt. % sodium hydride (101.0 g, 2.5 mol) andTHF (800 mL), ethyleneurea (EU) (100.0 g, 1.16 mol) was added atinternal temperatures of from 40 to 50° C. over 1 hour or longer,maintained at 50° C. for 1 hour. Allyl bromide (305.5 g, 2.5 mol) wasthen added dropwise at internal temperature of from 40 to 50° C. over 1hour, and the thus-obtained mixture was maintained at 53° C. for 1 hour.

Under cooling, methanol (50 mL) was gradually added at room temperature.The resulting mixture was filtered, and the thus-obtained filtrate wasconcentrated under reduced pressure. Hexane was added to the remainingresidue. Subsequent to thorough stirring, the mixture was filtered, andthe filtrate was concentrated under reduced pressure. Hexane was addedonce again to the residue, followed by thorough mixing. The mixture wasfiltered, and the filtrate was concentrated under reduced pressure toafford a concentration residue (109.8 g).

Finally, sodium sulfite (0.1 g) was added to the concentration residue,and reduced-pressure distillation was conducted to collect a fraction atfrom 95 to 105° C./0.12 kPa. As a result, N,N′-diallyl-ethyleneurea(DAEU) of 98% purity was obtained in an amount of 78.3 g (0.46 mol, pureyield: 40%/EU).

The followings are identification data of the thus-obtained DAEU:

¹H-NMR→See FIG. 45

MS spectrum→See FIG. 46

EXAMPLE 22

Synthesis of N-mono(allyloxycarbonyl)-ethyleneurea (abbreviated as“MACI”)

To a liquid mixture of pyridine (200.0 g, 2.5 mol), ethyleneurea (EU)(100.0 g, 1.16 mol) and dichloroethane (1,000 mL), allyl chloroformate(303.8 g, 2.52 mol) was added dropwise at internal temperatures of from25 to 30° C. over 0.5 hours or longer, and the resulting mixture wasmaintained under reflux (86 to 88° C.) for 6 hours.

Subsequent to cooling, dichloroethane (500 mL) and water (400 mL) wereadded. The resulting mixture was thoroughly mixed and allowed to stand,and an organic layer was separated. The thus-obtained organic layer waswashed with 16 wt. % saline, and a water layer was then removed. Theresulting organic layer was dried over magnesium sulfate, and filtered.The filtrate was concentrated under reduced pressure. Finally, theremaining residue was recrystallized from toluene, and then dried underreduced pressure to afford N-mono(allyloxycarbonyl)-ethyleneurea (MACI)of 88% purity (69.0 g, 0.36 mol, pure yield: 31%/EU).

The followings are identification data of the thus-obtained MACI:

¹H-NMR→See FIG. 47

MS spectrum→See FIG. 48

EXAMPLE 23

Synthesis of N,N′-di(allyloxycarbonyl)-ethyleneurea (abbreviated as“DACI”)

To a liquid mixture of 60 wt. % sodium hydride (50.0 g, 1.25 mol) andTHF (1,000 mL), ethyleneurea (EU) (50.0 g, 0.58 mol) was added atinternal temperatures of from 40 to 50° C. over 0.5 hours or longer,maintained at from 50 to 52° C. for 1 hour. To the mixture, allylchloroformate (150.7 g, 1.25 mol) was added dropwise at internaltemperatures of from 25 to 30° C. over 1.5 hours or longer, maintainedunder reflux (66° C.) for 2 hours.

After the reaction mixture was allowed to cool down to room temperature,insoluble matter was filtered off, and the filtrate was concentratedunder reduced pressure. Hexane (400 mL) and toluene (500 mL) were addedto the concentration residue, heated to 65° C. At the same temperature,insoluble matter was filtered off, and the filtrate was allowed toslowly cool down to room temperature to conduct recrystallization.Filtration was then conducted. Finally, hexane was added to thethus-obtained filter cake to perform sludgish precipitation. Theresulting mixture was filtered again, and the thus-obtained filter cakewas dried under reduced pressure to affordN,N′-di(allyloxycarbonyl)-ethyleneurea (DACI) of 92% purity (72.2 g,0.26 mol, pure yield: 45%/EU).

The followings are identification data of the thus-obtained DACI:

¹H-NMR→See FIG. 49

MS spectrum→See FIG. 50

EXAMPLE 24

Synthesis of N-mono(methacryloyl)-ethyleneurea (abbreviated as “EUM”)

To a liquid mixture of pyridine (158.2 g, 2.0 mol), ethyleneurea (EU)(172.2 g, 2.0 mol) and acetonitrile (1,000 mL), methacrylic acidchloride (209.1 g, 2.0 mol) was added dropwise at internal temperaturesof from 15 to 20° C. over 0.5 hours or longer, maintained at from 20 to25° C. for 3 hours.

The reaction mixture was then filtered, and the filtrate wasconcentrated under reduced pressure. The remaining residue was purifiedby chromatography on a silica gel column to give a crystalline residue.The residue was recrystallized from a mixed solvent of toluene andhexane to afford N-mono(methacryloyl)-ethyleneurea (EUM) of 99% purity(35.0 g, 0.23 mol, pure yield: 11%/EU).

The followings are identification data of the thus-obtained EUM:

¹H-NMR→See FIG. 51

MS spectrum→See FIG. 52

EXAMPLE 25

Synthesis of N,N′-di(methacryloyl)-ethyleneurea (abbreviated as “DMAI”)

To a liquid mixture of 60 wt. % sodium hydride (100.0 g, 2.50 mol) andTHF (1,600 mL), ethyleneurea (EU) (100.0 g, 1.16 mol) was added atinternal temperatures of from 40 to 50° C. over 2 hours or longer,maintained at from 40 to 50° C. for 4 hours. After the mixture wasallowed to cool down to room temperature, methacrylic acid chloride(250.0 g, 2.39 mol) was added dropwise at an internal temperature of 40°C. over 2 hours, maintained at 40° C. for 2 hours.

To the reaction mixture, methanol (50 mL) was carefully added atinternal temperatures of from 20 to 25° C. Subsequently, 35 wt. %hydrochloric acid (200 g) was likewise gradually added at internaltemperatures of from 20 to 25° C. The thus-obtained mixture was thenconcentrated under reduced pressure.

Hexane (1,000 mL) was then added to the concentration residue, followedby thorough mixing. After the mixture was allowed to stand, theseparated hexane layer was discarded. To the separated water layer,ethyl acetate (1,000 mL) was added, followed by thorough mixing. Afterthe mixture was allowed to stand, the separated ethyl acetate layer wascollected and concentrated again under reduced pressure.

Finally, toluene (800 mL) and hexane (800 mL) were added. Subsequent toheating under stirring, the mixture was subjected to hot filtration. Thefiltrate was slowly cooled to 5° C. to conduct recrystallization.Crystals were collected by filtration, and then dried under reducedpressure to afford N,N′-di(methacryloyl)-ethyleneurea (DMAI) of 95%purity (10.0 g, 0.043 mol, pure yield: 3.7%/EU).

The followings are identification data of the thus-obtained DMAI:

¹H-NMR→See FIG. 53

MS spectrum→See FIG. 54

EXAMPLE 26

Synthesis of N-methyl-N′-glycidyl-ethyleneurea (abbreviated as “MGI”)

Into a reaction flask, N-methyl-ethyleneurea (450.0 g, 4.05 mol),epichlorohydrin (2,082.0 g, 25.5 mol) and trimethylbenzyl chloride (15g) were charged. Under heating and reflux (115-120° C.), they werereacted for 5 hours, and the reaction mixture was cooled to 60° C.

A 39% aqueous solution of sodium hydroxide (625.0 g, 6.09 mol) was thenadded dropwise, followed by aging at 80° C. for 1 hour.

The reaction mixture was allowed to cool down to room temperature, andthen filtered. To the resulting filtrate, chloroform and water wereadded. After the resulting mixture was allowed stand, the chloroformlayer was collected. The thus-obtained chloroform layer was concentratedon an evaporator, and the residue was purified by silica gelchromatography. As a result, N-methyl-N′-glycidyl-ethyleneurea(abbreviated as “MGI”) of 92% purity was obtained in an amount of 56.2 g(0.33 mol, pure yield: 8.2%/N-methyl-ethyleneurea).

The followings are identification data of the thus-obtained MGI:

¹H-NMR→See FIG. 55

MS spectrum→See FIG. 56

EXAMPLE 27

Synthesis of N-methyl-N′-acryloyloxyethyl-ethyleneurea (abbreviated as“MAEI”)

To a liquid mixture of N-methyl-N′-(2-hydroxyethyl)-ethyleneurea (HEMI)(421 g, 2.90 mol), which had been synthesized fromchloroethyloxazolidone and methylamine, triethylamine (302 g, 2.98 mol)and chloroform (1,000 g), acrylic acid chloride (270 g, 2.98 mol) wasadded dropwise at internal temperatures of from 3 to 13° C. over 2 hoursor longer, followed by aging at from 5 to 12° C. for 2 hours. To thereaction mixture, chloroform and water were added to wash the same. Anorganic layer was separated and collected, and then washed withsaturated saline. An organic layer was obtained again and concentratedunder reduced pressure on an evaporator. Finally, the residue waspurified by chromatography on a silica gel column to affordN-methyl-N′-acryloyloxyethyl-ethyleneurea (abbreviated as “MAEI”) of 98%purity (261 g, 1.29 mol, pure yield: 44.5%).

The following is an identification datum of the thus-obtained MAEI:

¹H-NMR→See FIG. 57

EXAMPLE 28

Synthesis of N-acryloyl-oxazolidone (abbreviated as “ACOZ”)

To a liquid mixture of 2-oxazolidone (43.5 g, 0.50 mol) and acetonitrile(200 mL), β-chloropropionic acid chloride (65.4 g, 0.52 mol) was addeddropwise at internal temperatures of from 13 to 18° C. over 0.5 hours orlonger, maintained at 45° C. for 4 hours. After the mixture was cooledto 10° C., triethylamine (104.2 g, 1.03 mol) was added dropwise atinternal temperatures of from 10 to 20° C. over 1 hour or longer,maintained at 20° C. for 1 hour.

The thus-obtained reaction mixture was filtered, the filtrate wasconcentrated under reduced pressure, and chloroform (300 mL) and water(100 mL) were added to the concentration residue, followed by thoroughmixing. The resulting mixture was allowed to stand, and the organiclayer was collected.

The organic layer was then concentrated under reduced pressure, and theconcentration residue was purified by chromatography on a silica gelcolumn. As a result, N-acryloyl-oxazolidone (ACOZ) of 98% purity wasobtained in an amount of 20.5 g (0.14 mol, pure yield: 29%/oxazolidone).

The followings are identification data of the thus-obtained ACOZ:

¹H-NMR→See FIG. 58

MS spectrum→See FIG. 59

EXAMPLE 29

Synthesis of N-allyl-oxazolidone (abbreviated as “ALOZ”)

To a liquid mixture of 60 wt. % sodium hydride (20.0 g, 0.50 mol) andTHF (700 mL), 2-oxazolidone (43.5 g, 0.50 mol) was added at internaltemperatures of from 25 to 35° C. over 0.5 hours or longer, maintainedat 60° C. for 2 hours. After the mixture was allowed to cool down toroom temperature, allyl bromide (60.5 g, 0.50 mol) was added dropwise tothe mixture at internal temperatures of from 25 to 30° C. over 0.5 hoursor longer, maintained at 50° C. for 2 hours.

The thus-obtained reaction mixture was filtered, the filtrate wasconcentrated under reduced pressure, and the remaining concentrationresidue was purified by chromatography on a silica gel column. As aresult, N-allyl-oxazolidone (ALOZ) of 96% purity was obtained in anamount of 37.2 g (0.28 mol, pure yield: 56%/oxazolidone).

The followings are identification data of the thus-obtained ALOZ:

¹H-NMR→See FIG. 60

MS spectrum→See FIG. 61

EXAMPLE 30

Synthesis of N-vinyl-oxazolidone (abbreviated as “VOZ”)

Into a reaction flask, ethylene carbonate (176.1 g, 2.00 mol) anddiethanolamine (210.3 g, 2.00 mol) were charged. At from 160 to 165° C.,they were reacted for 5 hours. After cooling, the reaction mixture waspurified by chromatography on a silica gel column to afford crudeN-hydroxyethyl-oxazolidone (310 g).

To the crude product, potassium carbonate (6.9 g, 0.05 mol) and diethylcarbonate (945 g, 8.00 mol) were then added. They were reacted at from100 to 106° C. for 5 hours while drawing formed methanol. Subsequent tocooling, the reaction mixture was filtered, and the filtrate wasconcentrated under reduced pressure to afford crudeN-(ethylcarbonatoethyl)-oxazolidone (163 g).

The crude N-(ethylcarbonatoethyl)-oxazolidone was next added dropwiseunder reduced pressures of from 2.0 to 2.7 kPa (15 to 20 torr) into aflask which had been added with potassium carbonate (6.9 g, 0.05 mol)and was controlled at 190° C., and distilled fractions were collected.Finally, the thus-obtained fractions were distilled once again under areduced pressure of 1.3 kPa (10 torr), and a 120-130° C. fraction wascollected to afford N-vinyl-oxazolidone of 95% purity (63.0 g, 0.53 mol,pure yield: 26%/ethylenecarbonate).

The following is an identification datum of the thus-obtained VOZ:

MS spectrum→See FIG. 62

EXAMPLE 31

Synthesis of N-acryloyl-pyrrolidone (abbreviated as “NAPD”)

To a liquid mixture of 2-pyrrolidone (42.6 g, 0.50 mol) and chloroform(75 mL), β-chloropropionic acid chloride (65.4 g, 0.52 mol) was addeddropwise at internal temperatures of from 25 to 30° C. over 0.5 hours orlonger, maintained at 40° C. for 4 hours. After the mixture was cooledto 10° C., triethylamine (104.2 g, 1.03 mol) was added dropwise atinternal temperatures of from 10 to 20° C. over 1 hour or longer,maintained at 20° C. for 1 hour.

To the thus-obtained reaction mixture, chloroform (300 mL) and water(200 mL) were added, followed by thorough mixing. The resulting mixturewas allowed to stand, and the organic layer was collected.

The organic layer was then concentrated under reduced pressure, and theconcentration residue was purified by chromatography on a silica gelcolumn. As a result, N-acryloyl-pyrrolidone (NAPD) of 85% purity wasobtained in an amount of 50.5 g (0.31 mol, pure yield: 62%/pyrrolidone).

The followings are identification data of the thus-obtained NAPD:

¹H-NMR→See FIG. 63

MS spectrum→See FIG. 64

EXAMPLE 32

Synthesis of N-allyl-pyrrolidone (abbreviated as “ALPD”)

To a liquid mixture of 60 wt. % sodium hydride (40.0 g, 1.00 mol) andTHF (600 mL), 2-pyrrolidone (85.1 g, 1.00 mol) was added at internaltemperatures of from 24 to 33° C. over 1 hour or longer, maintained at60° C. for 2 hours. After cooling, allyl bromide (121.0 g, 1.00 mol) wasadded dropwise to the mixture at internal temperatures of from 30 to 35°C. over 1 hour or longer, maintained at 45° C. for 2 hours.

The thus-obtained reaction mixture was filtered, the filtrate wasconcentrated under reduced pressure, and the remaining concentrationresidue was purified by chromatography on a silica gel column. As aresult, N-allyl-pyrrolidone (ALPD) of 97% purity was obtained in anamount of 75.3 g (0.58 mol, pure yield: 58%/pyrrolidone).

The followings are identification data of the thus-obtained ALPD:

¹H-NMR→See FIG. 65

MS spectrum→See FIG. 66

EXAMPLE 33

Synthesis of N-allyl-N-methyl-acetamide (abbreviated as “ALACM”)

To a liquid mixture of 60 wt. % sodium hydride (40.0 g, 1.00 mol) andTHF (500 mL), N-methyl-acetamide (73.1 g, 1.00 mol) was added atinternal temperatures of from 21 to 27° C. over 40 minutes or longer,maintained at 60° C. for 2 hours. After cooling, allyl bromide (121.0 g,1.00 mol) was added dropwise to the mixture at internal temperatures offrom 29 to 31° C. over 40 minutes or longer, maintained at 50° C. for 2hours.

The thus-obtained reaction mixture was filtered, the filtrate wasconcentrated under reduced pressure, and the remaining concentrationresidue was purified by chromatography on a silica gel column. As aresult, N-allyl-N-methyl-acetamide (ALACM) of 97% purity was obtained inan amount of 65.0 g (0.56 mol, pure yield: 56%/N-methyl-acetamide).

The followings are identification data of the thus-obtained ALACM:

¹H-NMR→See FIG. 67

MS spectrum→See FIG. 68

EXAMPLE 34

Production of Polymer 1

To cyclohexane (50 mL) which had been bubbled with nitrogen,azobisisobutyronitrile (AIBN) (265 mg) was added, followed by bubblingwith nitrogen. MEMEU of 97% purity (20.0 g) was charged into theresultant mixture at an internal temperature of 20° C., and thermalpolymerization was conducted at 70° C. for 4 hours.

After completion of the polymerization, the solvent, cyclohexane, wasdecanted. To the remaining white solid, methanol (100 mL) was added todissolve the same. The thus-obtained solution was added dropwise understirring into diethyl ether (500 mL) which had been placed beforehand.The precipitated white solid was taken out and dried under reducedpressure.

As a result, an MEMEU polymer (17.3 g) of an average molecular weight of120,000 (converted based on polystyrene) as measured by GPC analysis wasobtained.

As a result of a measurement of this polymer by DSC, neither Tg nor Tmwas observed within a range of from −180 to 250° C. (1^(st)—Heat,1^(st)—Cool, 2^(nd)—Heat).

Concerning the solubility of the polymer in solvents, it was dissolvedat room temperature in ethanol and chloroform as desired (tested range:1 to 100 wt. %/solvent weight).

EXAMPLE 35

Production of Polymer 2

To a liquid mixture of N,N′-bis(methacryloyloxy-ethyl)-ethyleneurea(MEEU) of 97% purity (10.0 g) and N-methyl-N′-vinyl-ethyleneurea (MVI)(10.0 g), were added 2,2-dimethoxy-2-phenylacetophenone (100 mg, 0.5 wt.%) as a photopolymerization initiator, t-butyl peroxy-2-ethylhexanoate(60 mg, 0.5 wt. %) as a radical catalyst, anddi(5-n-butoxy-1,4-dimethyl-3-oxypentyl)phosphoric acid (60 mg, 0.5 wt.%) as an internal mold releasing agent. They were mixed, degassed underreduced pressure, and exposed to ultraviolet ray of from 100 to 130mW/cm² intensity for curing, and then annealed at from 80 to 120° C.

The thus-obtained resin was transparent, and its water contact angle was10°.

EXAMPLE 36

Production of Polymer 3

To a liquid mixture of N,N′-bis(acryloyloxyethyl)-ethyleneurea (AEEU) of96% purity (10.0 g) and N-methyl-N′-acryloyloxyethyl-ethyleneurea (MAEI)(10.0 g), were added 2,2-dimethoxy-2-phenylacetophenone (10 mg, 500 ppm)as a photopolymerization initiator, t-butyl peroxy-2-ethylhexanoate (40mg, 2,000 ppm) as a radical catalyst, anddi(5-n-butoxy-1,4-dimethyl-3-oxypentyl)phosphoric acid (40 mg, 2,000ppm) as an internal mold releasing agent. They were mixed, degassedunder reduced pressure, and exposed to ultraviolet ray of from 80 to 110mW/cm² intensity for curing, and then annealed at from 80 to 120° C. Thethus-obtained resin was transparent, and its water contact angle was 7°.

EXAMPLES 37-49

Production of polymers 4-16

Polymerization was conducted in a similar manner as in Example 35 orExample 36. Physical properties of the resultant resins are shown inTable-1.

COMPARATIVE EXAMPLES 1-4

Contact angles of commercially-available slide glass and general-purposeresins were measured. The results are shown in Table-1.

COMPARATIVE EXAMPLES 5-7

Polymerization was conducted in a similar manner as in Example 35 orExample 36. Physical properties of the resultant resins are shown inTable-1.

COMPARATIVE EXAMPLE 8

Resinification of acrylic acid was attempted under the conditions ofExample 36. Polymerization took place, but the resulting resin containednumeral crazing and cracks and was in a foamed form. Measurement of itscontact angle was not feasible.

TABLE 1 Example Polymer External Water contact Comp. Ex. No. Monomer-1Amount Monomer-2 Amount appearance angle Ex. 35 2 MEEU 10 parts MVI 10parts Transparent 10° 37 4 same as above 10 parts VP 10 partsTransparent  6° 38 5 same as above 10 parts ALPD 10 parts Transparent 7° 39 6 same as above 10 parts VOZ 10 parts Transparent 20° 40 7 sameas above 10 parts ALOZ 10 parts Transparent  9° 36 3 AEEU 10 parts MAEI10 parts Transparent  7° 41 8 same as above 10 parts DAEU 10 partsTransparent 15° 42 9 same as above 10 parts VOZ 10 parts Transparent  6°43 10 same as above 10 parts ALOZ 10 parts Transparent 20° 44 11 same asabove 10 parts MVA 10 parts Transparent 17° 45 12 S-3I 10 parts MVI 10parts Transparent  9° 46 13 EGMA 10 parts MVI 10 parts Transparent 12°47 14 same as above 10 parts MAEI 10 parts Transparent 18° 48 15 same asabove 10 parts ALPD 10 parts Transparent 17° 49 16 same as above 10parts MVA 10 parts Transparent 19° Comp. Ex.  1 Slide glass None 25°  2Nylon None 60°  3 Polycarbonate None 61°  4 Polypropylene None 81°  5EGMA 20 parts None Transparent 69°  6 same as above 10 parts HEMA 10parts Transparent 48°  7 same as above 10 parts Acrylic acid 10 partsTransparent 40° Abbreviations in the table are as will be definedhereinafter.

EXAMPLE 50

Production of Polymer 17

To a liquid mixture ofN,N′-bis{2-mercaptomethyl-2-(2-mercaptothio)-ethyl}-ethyleneurea (MESPI)of 98% purity (10.1 g) and bis(isocyanatomethyl)norbornane(NBDI) (9.9g), were added dibutyltin dichloride (6 mg, 300 ppm) as a catalyst,2-(2H-benzotriazol-2-yl)-4-(t-octyl)phenol (10 mg, 500 ppm) as anultraviolet absorber, di(5-n-butoxy-1,4-dimethyl-3-oxypentyl)phosphoricacid (60 mg, 3,000 ppm) as an internal mold releasing agent. They weremixed, degassed under reduced pressure, and subjected to thermalpolymerization at room temperature to 120° C. for 18 hours. Thethus-obtained resin board of 10 mm thickness was transparent, and had arefractive index of 1.62 (e beam; 546 nm), an Abbe number (e) of 39, Tg(TMA) of 137° C. and a density (d) of 1.30 (g/cc).

Further, the above-obtained resin was immersed at from 91 to 93° C. for60 minutes in a liquid mixture which consisted of dispersion dyes, “MLPBlue-2” (MITSUI BASF DYES LIMITED) (2.0 g), “MLP Red-2” (MITSUI BASFDYES LIMITED) (2.0 g) and “MLP Yellow-2” (MITSUI BASF DYES LIMITED) (4.0g), and water (1,000 mL). The resin was then taken out of the liquidmixture, washed and dried.

As a result, it was found that the resin had been dyed to 79% (beforethe dyeing test: 85%) in terms of transmission at 500 nm. The resultsare shown in Table-2.

COMPARATIVE EXAMPLE 9

Bis{2-mercaptomethyl-2-(2-mercaptothio)-ethyl}sulfide (FSH) (9.4 g) andbis(isocyanatomethyl)norbornane (NBDI) (10.6 g) were mixed, andsubjected to thermal polymerization in a similar manner as in Example42. The resulting resin board of 10 mm thickness was transparent, andhad a refractive index of 1.63 (e beam; 546 nm), an Abbe number (νe) of38, Tg (TMA) of 130° C. and a density (d) of 1.31 (g/cc).

Further, a dyeing test was conducted in a similar manner as in Example50. As a result, its transmittance at 500 nm was 84% (before the dyeingtest: 85%). The resin was not dyed under the conditions although itsheat resistance was lower than the resin of Example 50.

The results are shown in Table-2.

EXAMPLE 51

Production of Polymer 18

To a liquid mixture of N,N′-bis(thioglycidylthio-ethyl)-ethyleneurea(TGEU) of 99% purity (20.0 g) and N,N′-bis(mercaptoethyl)-ethylurea(DMEU) of 95% purity (1.0 g), triethylamine (21 mg, 1,000 ppm) was addedas a catalyst. Under reduced pressure, they were mixed and degassed. Thethus-degassed liquid mixture was charged in a mold and then graduallyheated from 25° C. to 120° C. over 20 hours to cure the polymerizablecompounds, and annealing was conducted at 120° C. for 2 hours. Thethus-obtained resin was transparent, and had a refractive index of 1.66(e beam; 546 nm), an Abbe number (νe) of 36, Tg (TMA) of 74° C. and adensity (d) of 1.32 (g/cc).

Further, the above-obtained resin was immersed at 92° C. for 3 minutesin a liquid mixture of a dispersion dye, “MLP Blue-2”, (MITSUI BASF DYESLIMITED), (5.0 g) and water (1,000 mL). The resin was then taken out ofthe liquid mixture, washed and dried. As a result, a resin evenly dyedin a dark blue color was obtained.

The results are shown in Table-2.

COMPARATIVE EXAMPLE 10

Bis(thioglycidyl) disulfide (abbreviated as “ETDS”) (18.0 g),bis{2-mercaptomethyl-2-(2-mercaptothio)-ethyl}sulfide (FSH) (2.0 g),N,N-dimethyl-cyclohexylamine (4 mg, 200 ppm) andN,N-dicyclohexyl-methylamine (20 mg, 1,000 ppm) and2-(2H-benzotriazol-2-yl)-4-(t-octyl)phenol (220 mg, 1.1 wt. %) weremixed, and subjected to thermal polymerization in a similar manner as inExample 28. The resulting resin board of 10 mm thickness wastransparent, and had a refractive index of 1.74 (e beam; 546 nm), anAbbe number (νe) of 33, Tg (TMA) of 80° C. and a density (d) of 1.46(g/cc). Dyeing of the above-obtained resin was attempted under theconditions of Example 51, but the resin was not dyed practically.

The results are shown in Table-2.

TABLE 2 Example Comp. Ex. Monomer-1 Amount Monomer-2 Amount Ne νe TgRemarks Ex. 50

10.1 parts

9.9 parts 1.62 39 137° C. Specific gravity: 1.30 Dyeing (T %: 85→79)Comp. Ex. 9

9.4 parts

10.6 parts 1.63 38 130° C. Specific gravity: 1.31 Dyeing (T %: 85→84)Ex. 51

20 parts

1 part 1.66 36  74° C. Specific gravity: 1.32 Dyed excellently Comp. Ex.10

18 parts

2 parts 1.74 33  80° C. Specific gravity: 1.46 Not dyed practically

EXAMPLE 52 COMPARATIVE EXAMPLE 11

(Water Absorption Test)

With respect to the resin of Example 37 and the resin of ComparativeExample 6, a submerged water absorption test was conducted (purifiedwater, 23° C.). The results are shown in Table-3.

TABLE 3 Percent weight increase after Exam- 5 hours ple Water (based onthe Comp. contact weight Ex. Monomer-1 Amount Monomer-2 Amount anglebefore test) Ex. 52

10 parts

10 parts  6° 116 wt % Comp. Ex. 11

10 parts

10 parts 48° 102 wt %

Industrial Applicability

The organic polymers according to the present invention are physicallyand chemically stable, and have high wettability, water (liquid)absorbing capability, transparency and dyeability. They can, therefore,be suitably used in the field of functional materials such asantifouling materials, anti-mist materials, dew preventing materials,water (liquid) absorbent materials and optical materials. Different fromthe conventional art, they do not require special ingenuity, apparatusand cumbersome conversion to assure high wettability and hightransparency.

What is claimed is:
 1. A polymerizable compound comprising, in amolecule thereof, one or more of the following partial structuralformula (A):

wherein A₁ to A₆each independently represent a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms, X₁represents O or S, and 1 stands foran integer of 0 to 2, and one or more thioepoxy groups orallylthio-carbonyl groups, or two or more allyloxycarbonyl groups, orone allyloxycarbonyloxy group or alloxycarbonylthio group.
 2. Apolymerizable compound comprising, in a molecule thereof, one or more ofthe following partial structural formula (A):

wherein A₁to A₆each independently represent a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms, X₁represents O or S, and 1 stands foran integer of 0 to 2, and two or more mercapto groups, glycidylthiogroups or (metb)acryloylthio groups.
 3. A polymerizable compoundrepresented by the following formula (B):

wherein A₁to A₆each independently represent a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms, X₁represents O or S, 1 stands for aninteger of 0 to 2, R₁ to R₄ each independently represent a hydrogenatom, a hydroxy group, a mercapto group, an alkyl group having 1 to 6carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthiogroup having 1 to 6 carbon atoms, or the below-described formulas (C) to(F), m and n each independently stand for an integer of from 0 to 10, Mand N each independently stand for an integer of from 1 to 10, R₅ and R₆each independently represent an alkoxy group having 1 to 6 carbon atoms,an alkylthio group having 1 to 6 carbon atoms, or the below-describedformulas (C) to (F), with a proviso that any one or more of R₁ to R₄ areany of the below-described formulas (C) to (E)

wherein A₇ represents a hydrogen atom or a methyl group, and X₂represents O or S;

wherein A₈ represents a hydrogen atom or a methyl group, and X₃ and X₄each independently represent O or S; and

wherein A₁ to A₆ each independently represent a hydrogen atom or analkyl group having 1 to 6 carbon atoms, X₁ or X₅ represents O or S, 1stands for an integer of 0 to 2, R₇ each independently represents ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkylgroup having 2 to 12 carbon atoms or an alkylthioalkyl group having 2 to12 carbon atoms, R₈ and R₉ each independently represent a hydrogen atom,a hydroxy group, a mercapto group, an alkyl group having 1 to 6 carbonatoms, an alkoxy group having 1 to 6 carbon atoms or an alkylthio grouphaving 1 to 6 carbon atoms, q stands for an integer of from 1 to 6, andr stands for an integer of an integer of from 0 to
 3. 4. A polymerizablecomposition comprising a polymerizable compound according to claim
 3. 5.An organic polymer available from polymerization of a polymerizablecompound according to claim 3 having a water contact angle of 20° orsmaller.
 6. An organic polymer available from polymerization of apolymerizable compound according to claim 5 having a water contact angleof 7° or smaller.
 7. A molded or otherwise formed product comprising anorganic polymer according to claim
 5. 8. A polymerizable compositioncomprising a polymerizable compound according to claim
 1. 9. Apolymerizable composition comprising a polymerizable compound accordingto claim
 2. 10. An organic polymer available from polymerization of apolymerizable compound according to claim 1 and having a water contactangle of 20° or smaller.
 11. An organic polymer available frompolymerization of a polymerizable compound according to claim 2 andhaving a water contact angle of 20° or smaller.
 12. An organic polymeravailable from polymerization of a polymerizable composition accordingto claim 4 and having a water contact angle of 20° or smaller.
 13. Anorganic polymer available from polymerization of a polymerizablecomposition according to claim 8 and having a water contact angle of 20°or smaller.
 14. An organic polymer available from polymerization of apolymerizable composition according to claim 9 and having a watercontact angle of 20° or smaller.
 15. An organic polymer according toclaim 10 wherein the organic polymer has a water contact angle of 7° orsmaller.
 16. An organic polymer according to claim 11 wherein theorganic polymer has a water contact angle of 7° or smaller.
 17. Anorganic polymer according to claim 12 wherein the organic polymer has awater contact angle of 7° or smaller.
 18. An organic polymer accordingto claim 13 wherein the organic polymer has a water contact angle of 7°or smaller.
 19. An organic polymer according to claim 14 wherein theorganic polymer has a water contact angle of 7° or smaller.
 20. A moldedor otherwise formed product comprising an organic polymer according toclaim
 10. 21. A molded or otherwise formed product comprising an organicpolymer according to claim
 11. 22. A molded or otherwise formed productcomprising an organic polymer according to claim
 12. 23. A molded orotherwise formed product comprising an organic polymer according toclaim
 13. 24. A molded or otherwise formed product comprising an organicpolymer according to claim 14.